State Department records show Richard Armitage, deputy secretary of state at the time, had a private hourlong meeting with Woodward, a reporter for The Washington Post, on June 13, 2003.
Woodward later said he learned from a source that Plame, the wife of a prominent Bush administration critic, worked for the CIA, The New York Times reports.
Plame's husband, former Ambassador Joseph Wilson, accused the Bush administration of twisting intelligence on Iraq's weapons programs before the U.S. invasion of Iraq.
Armitage and Woodward would not comment on the meeting. Neither would a spokesman for the special prosecutor in the politically important leak investigation.
Armitage also refused to say if he was the source about Plame to columnist Robert Novak, who first identified her as a CIA employee in a July 14, 2003, column.