In October 1861 White was at home on leave and riding in a buggy with a lady friend when he heard the opening shots of the Battle of Ball's Bluff; he rushed to the scene to join the fight. White was cited in several reports for his bravery and invaluable service in the battle. One officer reported, "I never witnessed more coolness and courage than this young gentleman displayed, being exposed to the heaviest fire of the enemy."

White was promoted to captain and authorized to raise a unit of partisans, who entered Confederate service in January 1862 as the 35th Battalion Virginia Cavalry and first served with General Stonewall Jackson in the Shenandoah Valley. White and his men aided the Confederate war effort in Virginia throughout the war, alternately as partisan rangers and in regular service, and fought in the Seven Days', Cedar Mountain, 2nd Bull Run, Antietam, Gettysburg, Mine Run, the Wilderness, Trevillian Station, and Petersburg battles. It was in the Mine Run campaign that General Thomas Rosser, after witnessing a vicious charge by White's screaming men, bestowed the nickname "Comanches" on the unit. When not performing regular service, they were raiding behind the Union lines. On one raid they traveled 700 miles in 21 days and destroyed 16 bridges. After the war, White returned to his farm and served as a sheriff, a banker, and a preacher.

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