In 1801, Governor John Sevier had reached the limit of three consecutive terms allowed as governor under the State Constitution of 1796, which Roane had helped to write while a delegate. He was elected as Sevier's successor. The Great Seal of Tennessee was adopted during the Roane Administration in 1801. Also during this term, Tennessee was divided into three Congressional districts.
While in office, any chance that Roane had to have a good relationship with former Governor Sevier was shattered when he cast a tie-breaking vote for Sevier's opponent, Andrew Jackson, in an election for a militia generalship. Sevier defeated Roane for re-election two years later, and wound up serving three more terms before again reaching the state constitution's term limits.