Following Georgia's secession, Thomas resigned his commission in the U.S. Army effective April 6, 1861. He was commissioned as a first lieutenant in the regularConfederate infantry on March 16, and promoted to major in the regular service that same day. In July Thomas was assigned to the 18th Alabama Infantry with the rank of major. Leaving the line service for staff work, Thomas was assigned to command the ordnance in the Confederate Department of Alabama & West Florida on December 20. In 1862 Thomas was sent to serve in the Western Theater, and was given command of the artillery belonging to a brigade in the Army of Mississippi as of March 18. Eight days later Thomas was appointed assistant inspector general of the brigade, a post he held until that summer. Assigned to the staff of Maj. Gen. Jones M. Withers, Thomas fought at the Battle of Shiloh on April 6-7, performing a "commendable part in the battle..." In July he was assigned command of the army's Reserve Corps artillery, a position Thomas would hold for the rest of the year. He also participated in the Kentucky Campaign that autumn, and then took a brief sick leave. Thomas returned to duty in time to fight during the Battle of Stone's River in late 1862. Beginning on January 2, 1863, Thomas was assigned as assistant inspector general of the Withers' Division in the renamed Army of Tennessee. Later in 1863, on the recommendation of Lt. Gen. Leonidas Polk, he was promoted to colonel and given command of the 12th Mississippi Cavalry. This new regiment, the reserve cavalry of Brig. Gen. James H. Clanton's Alabama Brigade, was also variously known as "Col. Thomas's Alabama Cavalry." On August 4, 1864, he was appointed as a "temporary" brigadier general of volunteer troops and that September was assigned brigade command in the defenses in Mobile, Alabama. His appointment was never confirmed by the Confederate Congress so his actual highest grade was colonel.
In 1865 Thomas participated in the Mobile Campaign as part of the Confederate force holding Fort Blakely in Baldwin County, Alabama. Beginning on April 1 Thomas and the fort was put under siege by the Union forces of Maj. Gen. Edward R. S. Canby. His command—mostly consisting of "boy reserves"—held the right of the Confederate works, on the left was the division of Brig. Gen. Francis Cockrell, and both under Brig. Gen. St. John Richardson Liddell, the garrison commander. At 5:30 p.m. on April 9 the attack came, with simple numbers deciding the assault, which lasted only 20 minutes. In the fight, 3,700 Confederates, Thomas, Cockrell, as well as Liddell were all captured. Thomas was held until June when he was released from Fort Gaines, Alabama, paroled and returned home.
Postbellum career
After the American Civil War, Thomas worked as a farmer in Dooly County and then Whitfield County, Georgia. He then worked as a deputy U.S. Marshal, and in 1884 he founded a private academy. Finally settling in Dalton, Thomas served as superintendent of the city's schools from 1891 to 1900. He died in Dalton in 1905 and was buried in the city's West Hill Cemetery. The Bryan M. Thomas Chapter of the United Daughters of the Confederacy was named in his honor.
Personal
In 1865, Thomas married Mary Jones Withers, the daughter of Maj. Gen. Jones M. Withers, his first commander. Together they had a daughter named Harriet.