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Update:  David Shuster is reporting that Rove was questioned extensively today regarding  Viveca Novak's supposedly exculpatory conversation with Robert Luskin. 

Karl Rove's history of appearing before the Grand Jury was largely unknown until he testified for what is believed to be the third time in October of 2004. 

Fitzgerald took over the case in January of 2004 and immediately issued a number of subpoenas for documents pertaining to the case.  He also specifically subpoenaed Matt Cooper regarding his July 2003 article, A War on Wilson.  But since Rove had not issued a waiver for Cooper to speak to Fitzgerald, he obviously thought he was in the clear when he initially spoke to the FBI (recap here) and the grand jury, and that Cooper would be the firewall between him and Fitzgerald.

First Grand Jury Appearance:  February, 2004

We now know that  Rove's first appearance happened in February of 2004, according to the Washington Post on December 3, 2005:

One person familiar with the case said the [Viveca] Novak-Luskin conversation is not what prompted Rove to change his testimony in the case. In fact, this person said, Novak told Luskin about the Rove-Cooper connection before Rove's first appearance before the grand jury in February 2004. In that appearance, Rove testified that he did not recall talking to Cooper about Plame. It was not until October 2004 that Rove told the grand jury he recalled the Cooper chat.

Set aside the Vivac-Luskin stuff for the moment because that's a conversation unto itself.  What did Rove say when he appeared?  According to the NYT (11/4/05):

In his testimony to the grand jury in February 2004, Mr. Rove did not disclose the conversation with Mr. Cooper, saying later that he did not recall it among the hundreds of calls he received on a daily basis.

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In February 2004, when Mr. Rove testified about his conversations with reporters, he recalled the [Robert] Novak conversation, but no other interviews with reporters -- an omission that Mr. Fitzgerald has investigated as a possible false statement or perjury. Mr. Rove said he had forgotten the discussion with Mr. Cooper, the lawyers said.

Mr. Fitzgerald did not learn of the Cooper conversation until months later when a search of Mr. Rove's e-mails uncovered the e-mail that he had sent to Mr. Hadley. ''Matt Cooper called to give me a heads-up that he's got a welfare reform story coming,'' Mr. Rove wrote in the message to Mr. Hadley that was first disclosed in July by the Associated Press.

''When he finished his brief heads-up he immediately launched into Niger,'' Mr. Rove wrote. ''Isn't this damaging? Hasn't president been hurt? I didn't take the bait, but I said if I were him I wouldn't get Time far out on this.''

Matt Cooper got a waiver from Libby and gave a deposition to Fitzgerald in August, 2004.  On July 23, 2005 VandeHei and Leonnig writing in the Washington Post reported that at that time Fitzgerald was surprised to learn that Libby was not Cooper's original source:

Lawyers involved in the case said there are now indications that Fitzgerald did not initially know or suspect that Rove was Cooper's primary source for the reporter's information about Plame. That raises questions about how much Rove disclosed when first questioned in the inquiry or how closely he was initially queried about his contacts with reporters.

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Also, when first questioned in the days after Plame's name appeared in the press, Rove left the impression with top White House aides that he had talked about her only with Novak, according to a source familiar with information provided to investigators.

Initially, Fitzgerald appeared focused on the theory that Libby had leaked Plame's identity, according to lawyers involved in the case. He had interviewed three other reporters about their conversations with Libby, but all three indicated he either did not discuss Plame or did not reveal her identity.

He also sought testimony from Cooper about his July 2003 story in Time. In 2004, Cooper obtained a waiver from Libby to discuss their conversation, as had the three other reporters.

Cooper and his attorneys were surprised that Fitzgerald agreed to ask Cooper questions only about his conversations with Libby, sources familiar with the investigation said.

The sources said Fitzgerald looked surprised in the August 2004 deposition when Cooper said it was he who brought up Wilson's wife with Libby, and that Libby responded, "Yeah, I heard that, too."

The prosecutor pressed Cooper to then explain how he knew about Wilson's wife in the first place, and Cooper said he would not answer the question because it did not involve Libby, the sources said.

Second or Third Appearance:  October 15, 2004

Viveca Novak, writing in Time Magazine said that Rove made his third appearance before the grand jury on October 15.  Rove evidently volunteered to testify this time, but the testimony came two days after Judge Thomas Hogan found Matt Cooper in contempt of court for the second time for refusing to testify and it became apparent that Cooper would in fact have to reveal that Rove was his source.*

Said Gold Bars at the time:

"My client appeared voluntarily before the grand jury and has cooperated with the investigation since it began," said Rove's attorney Robert Luskin. "He has been assured in writing as recently as this week that he is not a target of the investigation."

From the Washington Post, 12/03/05:

It was not until October 2004 that Rove told the grand jury he recalled the Cooper chat.

And according to VandeHei and Leonnig in the Washington Post on October 20, during this appearance Rove may have ratted out Libby:

White House adviser Karl Rove told the grand jury in the CIA leak case that I. Lewis "Scooter" Libby, Vice President Cheney's chief of staff, may have told him that CIA operative Valerie Plame worked for the intelligence agency before her identity was revealed, a source familiar with Rove's account said yesterday.

In a talk that took place in the days before Plame's CIA employment was revealed in 2003, Rove and Libby discussed conversations they had had with reporters in which Plame and her marriage to Iraq war critic Joseph C. Wilson IV were raised, the source said. Rove told the grand jury the talk was confined to information the two men heard from reporters, the source said.

Rove has also testified that he also heard about Plame from someone else outside the White House, but could not recall who.

Fourth Appearance:  October 14, 2005

According to Newsweek, this appearance before the Grand Jury evidently dealt with the discrepancies between Rove's testimony and that of Matt Cooper and also with the Hadley email that surfaced between Rove's third and fourth appearances (quite belatedly, as it seems to have been in response to Fitzgerald's initial subpoenas of January 2004):

In Cooper's account, Rove told him the wife of White House critic Joseph Wilson worked at the "agency" on WMD issues and was responsible for sending Wilson on a trip to Niger to check out claims that Iraq was trying to buy uranium. But Rove did not disclose this conversation to the FBI when he was first interviewed by agents in the fall of 2003—nor did he mention it during his first grand jury appearance, says one of the lawyers familiar with Rove's account. (He did not tell President George W. Bush about it either, assuring him that fall only that he was not part of any "scheme" to discredit Wilson by outing his wife, the lawyer says.) But after he testified, Luskin discovered an e-mail Rove had sent that same day—July 11—alerting deputy national-security adviser Stephen Hadley that he had just talked to Cooper, the lawyer says. In the e-mail, Rove said Cooper pushed him on whether the president was being hurt by the Niger controversy. "I didn't take the bait," Rove wrote Hadley, adding that he warned Cooper not to get "far out in front on this." After reviewing the e-mail, Rove then returned to the grand jury last year and reported the Cooper conversation. He testified that the talk was initially about "welfare reform"—a topic mentioned in the e-mail—and that Cooper then changed the subject. Cooper has written that he doesn't recall a discussion of welfare reform.

Why didn't the Rove e-mail surface earlier? The lawyer says it's because an electronic search conducted by the White House missed it because the right "search words" weren't used. (The White House and Fitzgerald both declined to comment.)

The Washington Post also reported that there were other discrepancies between Rove's and Cooper's testimony regarding their conversation:

Besides Cooper, at least two other people have testified before the grand jury since Rove last answered questions: New York Times reporter Judith Miller, who was questioned after initially refusing to appear and serving 85 days in jail, and Rove's secretary.

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Rove's secretary was questioned about why a phone call from Cooper to Rove in 2003 was not recorded in White House phone logs, according to sources familiar with the probe. She reportedly explained that Cooper called the main switchboard and his call was not logged because it was rerouted to Rove's office.

One apparent conflict between Rove's and Cooper's accounts centers on Rove telling the grand jury that he and Cooper talked primarily about welfare during their conversation, according to lawyers familiar with Rove's account. Cooper has said the grand jury asked him repeatedly about the welfare portion of his discussion with Rove, but Cooper said that, although he left a message for Rove about welfare reform, their conversation that day centered on Wilson.

Since Rove's fourth appearance, the most notable thing to have become public is the conversation between Viveca Novak and Robert Luskin that Team Rove say puts him in the clear.  There are a many conflicting stories about these particular events which Luskin claimed at the time provided a perfectly reasonable explanation for why his client did not find the Hadley email until long after he was aware of the original subpoenas.  Luskin also claimed that the Viveca Novak conversation was the the reason Rover had his memory jarred.  The Viveca Novak story is a long and convoluted one but if it is as Luskin said part of Rove's defense for his faulty memory, Rove was no doubt questioned about it during his four hours with Mr. Fitzgerald today.

Note:   Pollyusa's kos diary of last year is indispensable in the reconstruction of these appearances, and  there is a persuasive argument made in the comments that Rove's third trip to the grand jury happened in July of 2005.

*  Paul Lukasiak also reminds me that Rove's "offer" to testify came after Time Magazine said they would hand over Matt Cooper's notes.