Angry Republicans boycotted the vote and staged a walkout.
The vote was 223-32 to hold White House chief of staff Josh Bolten and former White House counsel Harriet Miers in contempt. The citations charge Miers with failing to testify and accuse her and Bolten of refusing Congress' demands for documents related to the 2006-2007 firings.
Republicans said Democrats should instead be working on extending a law - set to expire Saturday - allowing the government to eavesdrop on phone calls and e-mails in the United States in cases of suspected terrorist activity.
"We have space on the calendar today for a politically charged fishing expedition, but no space for a bill that would protect the American people from terrorists who want to kill us," said Minority Leader John A. Boehner, R-Ohio.
"Let's just get up and leave," he told his colleagues, before storming out of the House chamber with scores of Republicans in tow.
The vote, which Democrats had been threatening for months, was the latest wrinkle in a more than yearlong constitutional clash between Congress and the White House. The administration says the information being sought is off-limits under executive privilege, and argues that Bolten and Miers are immune from prosecution.
Democrats said they were acting to protect Congress' constitutional prerogatives.
"No one is immune from accountability and the rule of law, not Harriet Miers or Josh Bolten, and especially not President Bush or Vice President Cheney," said Rep. Robert Wexler, D-Fla.
The White House said the Justice Department would not ask the U.S. attorney to pursue the House contempt charges. However, the measure would allow the House to bring its own lawsuit on the matter.
It is the first time in 25 years that a full chamber of Congress has voted on a contempt of Congress citation, and the White House quickly pointed out that it was the first time that such action had been taken against top White House officials who had been instructed by the president to remain silent to preserve executive privilege.
"This action is unprecedented, and it is outrageous," Dana Perino, Bush's spokeswoman, said in a lengthy and harshly worded statement after the vote. "It is astonishing and deeply troubling that after months of delay on passing a bill that will help our intelligence professionals monitor foreign terrorists who want to kill Americans, the House has instead turned its attention to the silly, pointless, and unjust act of approving these contempt resolutions."
If Democrats bring suit to press the contempt charges, Perino added, "they will be met with opposition at the courthouse door and at every step of the way."
House Republicans argued that there had been no evidence of wrongdoing in the prosecutors flap, and called the vote a waste of time that would actually damage Congress' standing.
"We don't have evidence that we can give to the U.S. attorney. What we're giving to him is the desire to continue a witch hunt which has produced up to today zero - nothing," said Rep. Chris Cannon, R-Utah.
Under former Attorney General Alberto Gonzales, Justice Department officials consulted with the White House, fired at least nine federal prosecutors and kindled a political furor over a hiring process that favored Republican loyalists.
Bush's former top political adviser, Karl Rove, has also been a target of Congress' investigation into the purge of prosecutors, although Thursday's measure was not aimed at him.
Fred Fielding, the current White House counsel, has offered to make officials and documents available behind closed doors to the congressional committees probing the matter - but off the record and not under oath. Lawmakers demanded a transcript of testimony and the negotiations stalled.
The contempt debate sparked an unusually bitter scene even in the fractious House. Democrats accused Republicans of marring the Capitol memorial for their fallen colleague Rep. Tom Lantos, D-Calif., by interrupting it with a protest vote. GOP leaders shot back that it was Democrats who were responsible for dishonoring Lantos, by calling the House into session for the contempt debate before the service had ended.
It's not clear that contempt of Congress citations must be prosecuted. The law says the U.S. attorney "shall" bring the matter to a grand jury.
In 1982, the House voted 259-105 in 1982 for a contempt citation against Environmental Protection Agency Administrator Anne Gorsuch, but the Reagan-era Justice Department refused to prosecute the case.
The Justice Department also sued the House of Representatives in that case, but the court threw out the suit and urged negotiation. The Reagan administration eventually agreed to turn over the documents.
The last time a full chamber of Congress voted on a contempt of Congress citation was 1983. The House voted 413-0 to cite former EPA official Rita Lavelle for contempt of Congress for refusing to appear before a House committee. Lavelle was later acquitted in court of the contempt charge, but she was convicted of perjury in a separate trial.
On Thursday, three Republicans joined 220 Democrats to support the contempt resolution, including Rep. Walter B. Jones of North Carolina, presidential candidate Rep. Ron Paul of Texas and Rep. Wayne T. Gilchrest of Maryland, who was defeated this week in a primary. One Republican, Rep. Jon Porter of Nevada, voted "present."
