Multiple people familiar with the meeting told ABC News the interview happened Monday.
A source told Politico the team questioned Spicer about FBI Director James Comey's firing, statements Spicer made about the firing and President Donald Trump's meeting with Russian Foreign Minister Sergei Lavrov in the White House.
Mueller is investigating whether the Trump campaign colluded with Moscow to interfere in the 2016 presidential election, the firing of Comey as well as a statement Trump made about Donald Trump Jr.'s meeting with a lawyer at one time linked to the Russian government.
Deputy Attorney General Rod Rosenstein appointed Mueller, former director of the FBI, to lead the Justice Department's investigation after Attorney General Jeff Sessions recused himself.
Mueller's team has been in the midst of talking to current and former White House staff about the probe in the coming weeks. The team spoke to National Security Council chief of staff Keith Kellogg as well as former White House chief of staff Reince Priebus.
Mueller has said he's interested in also speaking to communications director Hope Hicks, White House counsel Don McGahn, communications adviser Josh Raffel and associate counsel James Burnham.
Meanwhile, the Senate intelligence committee, in a simultaneous probe into Russia, subpoenaed documents and testimony from former Trump adviser Carter Page, a source told NBC News on Tuesday. Committee members expect Page will invoke the Fifth Amendment.