US Attorney General Jeff Sessions was questioned by investigators examining whether Russia colluded with the Trump campaign in the 2016 election.
A Department of Justice (DOJ) spokeswoman confirmed to the BBC that the meeting took place last week.
Mr Sessions appears to be the first member of President Donald Trump's cabinet to be questioned.
Former FBI director Robert Mueller is leading the inquiry into alleged Russian meddling in the 2016 election.
He is also investigating whether Mr Trump's firing of FBI director James Comey last year was an effort to obstruct the agency's Russia probe.
The interview with Mr Sessions, the nation's top justice official, lasted several hours, according to US media reports.
Seventeen US intelligence agencies have concluded that Russia sought to aid Mr Trump's electoral victory, but it has not been proven that Trump campaign officials colluded with the Kremlin. Mr Trump has denied any wrongdoing.
The former FBI director, as well as three different congressional committees, are investigating the allegation of Russian meddling, and possible collusion.
Heading toward a face-off with Trump?
Anthony Zurcher, BBC News, Washington
Robert Mueller's investigation has now reached into Donald Trump's Cabinet.
While this is a significant development, it shouldn't come as a major surprise given that Jeff Sessions sits at the intersection of multiple reported threads of the inquiry. The former senator had contact with Russians while he was senior adviser to the Trump campaign. Later he was less than forthcoming about their nature.
Mr Sessions also may know details about why the president fired FBI Director James Comey, which could be a key component of any obstruction of justice cases Mr Mueller is building against the president or his staff.
With the Sessions interview – and recent news that Steve Bannon will also speak with Mr Mueller – there are only a handful of top Trump advisers who served in both the administration and the campaign who have yet to have received a visit from the special counsel's office. Vice-President Mike Pence is one. Donald Trump Jr and Ivanka Trump are two others.
Then there's the president himself.
Mr Mueller's investigation appears to be heading toward a face-off with the president. Then it will be time for the former top FBI man to put his cards on the table.
Mr Sessions, who oversees the FBI at the DOJ, recused himself from the investigation in March 2017 after he acknowledged two previously undisclosed meetings with a Russian ambassador during the campaign.
The president repeatedly criticised Mr Sessions for his recusal on Twitter.
The former Alabama senator could be an important witness due to his ties to the firing of Mr Comey.
The White House initially said that the FBI director's sacking was on the recommendation of the justice department, citing a DOJ memo faulting Mr Comey's handling of the investigation into Hillary Clinton's private email server.
But Mr Trump later said he was thinking of "this Russia thing" in Mr Comey's firing.
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