George W. Vail was the oldest son of Cornwall shoemaker Philander Vaill and Urena (Johnson) Vaill. George had left home early to apprentice with a Litchfield millwright when he was 12 or 14. He was working as a painter in Torrington in 1860, but listed Cornwall as his residence when he enlisted.

Vail appears to have been the first man from Cornwall to enlist during the Civil War, signing up with the 4th Connecticut Volunteer Infantry (later the 1st Connecticut Heavy Artillery) on May 23, 1861. His brothers, John Randolph Vaill and Henry Lyman Vaill, also served during the Civil War.

After the war, Vail returned to Torrington to work in the furniture trade, later establishing a flour and feed business. Vail married Ella M. Smith; the couple had two children.