 In 1831, Breathitt was one of several candidates put before the General Assembly to succeed John Rowan in the United States Senate. He received 66 of 137 votes, 3 votes short of a majority. Other unsuccessful nominees included John J. Crittenden (68 votes), Richard Mentor Johnson (64 votes), and Charles A. Wickliffe (49 votes). After 15 ballots, the Assembly still had not chosen a nominee, and postponed the matter until the next session. At that session, Henry Clay was chosen to fill the seat.
