The family moved to Greene County, Alabama, in 1822. The younger Maxwell graduated from the University of Virginia in 1841, studied law in Alabama, and was admitted to the Alabama bar in 1843. Maxwell was a Democrat and a vestryman in the Episcopal church.
He had three children by his 1843 marriage to Sarah Roane Brockenbrough and, after her death, five children by his 1853 marriage to Julia H. Anderson. Maxwell practiced law in Eutaw, Alabama, from 1843 to 1845, when he moved lo Tallahassee, Florida. With help from his Brockenbrough in-laws, he entered public life and was attorney general of Florida in 1846-1847, a member of the state House in 1847, secretary of state in 1848, state senator in 1849-1850, and U.S. congressman from 1853 to 1857.
He left Congress in 1857 and practiced law in Pensacola, Florida. From 1857 to 1861, he was a U.S. naval agent at Pensacola. He supported secession.
Maxwell was elected to the Confederate Senate and served from 1862 to 1865. An administration supporter, he feared excessive speculation on war goods. He was involved in the peace movement of 1864.
He served on the Commerce, Patents, Engrossment and Enrollments, Foreign Affairs, Indian Affairs, and Naval Affairs Committees. In 1865-1866, he was a judge of the Florida Supreme Court, but resigned in late 1866 to become president of the Pensacola and Montgomery Railroad and the law partner of Stephen Mallory. From 1877 to 1885, he was appointed a state circuit court judge.
In 1885, he was a delegate to the state constitutional convention, and from 1887 to 1891, he was chief justice of the Florida Supreme Court. He then retired from public life but resumed his law practice in Pensacola.
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