The American leader has always been an outspoken supporter of same-sex marriage despite his own faith being opposed to it.
He got a special temporary certification from the District of Columbia to allow him to conduct the wedding of his two aides Joe Mahshie and Brian Mosteller.
A White House spokesperson confirmed the couple had asked Mr Biden to officiate.
The vice president agreed to host the wedding at this home in Washington DC.
Gay marriage was made legal in America after a Supreme Court ruling in 2015.
Many Christians argue it is unbiblical and against the teachings of God.
