In early 1861, the Southern states that had seceded from the Union appointed special commissioners to travel to those other slaveholding Southern states that had yet to secede. Bonham served as the Commissioner from South Carolina to the Mississippi Secession Convention, and helped to persuade its members that they should also secede from the Union.
Bonham was appointed major general and commander of the Army of South Carolina by Gov. Francis W. Pickens in February 1861. He was appointed brigadier general in the Confederate Army on April 19, 1861, and commanded the First Brigade of the Confederate "Army of the Potomac" under P.G.T. Beauregard. He fought in the First Battle of Manassas, commanding his brigade as well as two artillery batteries and six companies of cavalry in the defense of Mitchell's Ford on Bull Run.
He resigned his commission January 27, 1862, to enter the Confederate Congress. On December 17, 1862, the South Carolina General Assembly elected Bonham as governor by secret ballot. He served until December 1864. During his term, the General Assembly enacted a prohibition against distilling in 1863 and also that year, it demanded that more land be used to grow food instead of cotton to increase the supply of food in the state. Bonham rejoined the Confederate Army as brigadier general of cavalry in February 1865, and was actively engaged in recruiting when the war ended.
Near Greenville, South Carolina a group of troops positioned there, because of worry of federal invasion from North Carolina, named their emplacement, Camp Bonham, in his honor.
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