Kerry, a Democratic ally of the White House who chairs the Senate Foreign Relations Committee, said he would make a public appearance with Jibril at 3:30 pm (1930 GMT).
"The Foreign Relations Committee and the American people are eager to learn more about the opposition movement in Libya and Mahmud Jibril is well positioned to answer our questions," Kerry said in a statement.
US lawmakers have said they are eager to pursue efforts to better understand the Libyan opposition in talks with Jibril, who handles foreign policy for Libya's National Transitional Council (NTC).
Kerry had invited Jibril to Washington when they met in Cairo in March, but the Libyan canceled a planned mid-April US visit.
Unlike France, Italy and Qatar, the United States has not recognized the NTC. Washington says it wants to obtain a "clearer picture" of who they are first.