During the American Civil War, Vance served in the Confederate States Army, where he reached the rank of brigadier general.

Vance was born in 1828, near present-day Weaverville, in the old homestead on Reems Creek, at Buncombe County, North Carolina.

When he was twelve, his father owned 12 slaves, the names of which eight are known – Sandy, Leah, Ann, Aggy, May, Bob, Richard and Venus.

"[10][11] In total, the slaves tended to the Vance children, cooked the family's meals, made the housing wares, fetched the water, cultivated the farm crops, and, otherwise, allowing Vance to spend his formative years pursuing his education and reading the classics from a 500-volume library that his family inherited from his uncle.

[2] When Vance was twenty, he was elected clerk of the Buncombe County Court of Common Pleas and Quarter Sessions, the position his father held until his death.

[2] Vance entered the Confederacy forming the "Buncombe County Life Guards" (later, Company H of the 29th North Carolina Infantry Regiment).

[2] They later accompanied Edmund Kirby Smith into Kentucky, and on December 30, 1862, Vance commanded the brigade of James E. Rains, after his death, at the Battle of Murfreesboro.

[2][14] After a lengthy recovery from his illness, Vance was placed in charge of the North Carolina–Tennessee mountains under the command of General Braxton Bragg, with orders to harass the Union flanks and disrupt the flow of enemy supplies.

On March 10, 1865, Lincoln granted Vance a conditional full pardon, allowing him to return to North Carolina, but requiring him not to fight again.

[15][16] While in office, he obtained appropriations for every county in his district to get daily mail delivery, and to have the French Broad River dredged from Brevard to Asheville for transportation.