George W. Melvin was born around 1837 in Mississippi to Joshua Melvin. His father was a farmer who owned $2,300 of real estate in 1850. The family moved to Bienville Parish, Louisiana, in the 1840s, and Melvin grew up and attended school there. He enrolled in the preparatory department in Mount Lebanon University.
He enlisted in the Confederate army on July 7, 1861, and mustered in as a corporal in Company C of the 9th Louisiana Infantry. He eventually earned a promotion to 3rd lieutenant. Union forces captured him on November 7, 1863, and he spent the rest of the war imprisoned in the Old Capital Prison in Washington, D.C., and at Johnson’s Island. He returned to Bienville Parish after the war, and he married Anna E. Theus there on October 19, 1865. He probably died around 1878.