George Baylor was born on February 13, 1842 at "Wood End," Jefferson County, Virginia. He was one of three sons of Colonel Robert William Baylor, who led the Virginia cavalry militia in defense of Harper's Ferry during John Brown's Raid in October 1859. The younger Baylor was schooled at the Charlestown Academy and enrolled at Dickinson College in Carlisle, Pennsylvania in 1857. There, he became a member of the Phi Kappa Psi fraternity and was elected to the Union Philosophical Society. He graduated with his class in the early summer of 1860 and took a position as an assistant teacher under his old academy instructor, R. Jaquelin Ambler, at the Clifton High School near Markham in Farquier County, Virginia.
At the outbreak of the Civil War, Baylor enlisted in May 1861 as a private in Company G of the Second Virginia Infantry and fought as part of the "Stonewall Brigade" at the Battle of First Manassas. In early 1862, he joined the company of cavalry his father had raised, called "Baylor's Light Horse," which became Company B of the Twelfth Virginia Cavalry. He was appointed third lieutenant and, following action in the Shenandoah Valley, took command of the company after his father was wounded and captured. From then on, the young Baylor gained a reputation as one of the most resourceful junior cavalry leaders of the war. He himself was wounded and captured during a raid in February 1863, but was exchanged in April of that year and rejoined his men. As part of Stuart's Cavalry Corps, the Twelfth Virginia took part in almost constant action during 1863. At Warrenton Springs, Baylor's company won the singular honor of a ten-day furlough on the personal order of General Lee for a remarkable charge across a stream that turned the day. Baylor was wounded again with a gunshot wound to the shoulder during a raid on enemy wagons at Medley, Virginia in January 1864. He did not return to action until May 1864, when his unit opened the Battle of the Wilderness.
Baylor's subsequent raiding further enhanced his reputation, especially when he attacked a unit of the Twelfth Pennsylvania Cavalry in his hometown of Charlestown, capturing twenty-seven men and horses. In April 1865, he joined Mosby's Cavalry as commander of Company H of the Forty-third Virginia Cavalry and continued raiding along communication lines. On at least one of these occasions, he faced a fellow Dickinsonian. On April 10, 1865, Colonel Charles Albright, class of 1852, reported that he had met a raid from Captain Baylor and "whipped him like thunder." Baylor also initiated an enduring Dickinson legend in May 1864 while in pursuit of Union forces withdrawing from their raid on Trevilan. During this conflict, he was hit in the chest with a bullet that struck the Union Philosophical Society badge he always wore on his uniform. He thought he had been killed, but one of his men was able to remove the spent ball, for it had barely broken the skin. The bullet tore the shield off the badge and bent its Maltese cross, but the talisman took much of the remaining force from what was probably already a fairly spent round. When the end of the war came, Baylor surrendered at Winchester on May 8, 1865. His two eldest brothers died in action during the war.
When Baylor returned to civilian life, he completed a law degree at Washington and Lee College in 1867 and then moved to Kansas City, Missouri to practice. After five years in the West, he returned home to Charlestown and built a lucrative law practice with William L. Wilson. Baylor also served a four-year term as prosecuting attorney for Jefferson County. He later became the chief legal counsel for the Baltimore and Ohio Railroad, the line that he had raided with such enthusiasm as a young man.
In April 1872, Baylor married Lalia Louise Beatty of Maryland. George Baylor died on March 6, 1902 and was buried in the Zion Episcopal Church Cemetery in Charlestown, West Virginia. He was sixty years old.