After the war he studied law under his uncle Jesse Bledsoe, and practiced law in Kentucky.
He served in the Kentucky militia during the War of 1812. In Alabama he practiced law and continued his political career. In 1824 he was elected to the Alabama House of Representatives.
Baylor was elected as a Jacksonian to the Twenty-first Congress (March 4, 1829 – March 3, 1831) from Alabama"s 2nd congressional district and was an unsuccessful candidate for election in 1830 to the Twenty-second Congress.
In 1836 Baylor fought as a lieutenant colonel against the Creek tribe in the Creek War of 1836. At the age of 46, Baylor moved to Texas, where he would live for the rest of his life.
He quickly made a name for himself in Texas law as judge of the Third Judicial District of the Congress of the Republic of Texas, and was appointed to the Texas Supreme Court as an associate justice in 1841, a position he would hold until the annexation of Texas in 1845. Baylor was one of the first officers of the Texas Baptist Educational Society and, in 1844, along with Reverend William Tryon and Reverend James Huckins, sent a petition to the Congress of the Republic of Texas asking the nation to charter a Baptist university.
In response to this petition, The Republic of Texas produced an Acting of Congress that was signed on February 1, 1845, by Anson Jones, providing the charter that yielded Baylor University and, later, the University of Mary Hardin-Baylor.
He was briefly a member of the Kentucky House of Representatives from 1819 to 1820 before he resigned and moved to Alabama.