Marley White was born around 1844 in Charlottesville, Virginia, and worked as a farmer before the Civil War. He enlisted in the Union army in Vicksburg, Mississippi, on March 10, 1864, and mustered in as a private in Company F of the 66th USCT Infantry Regiment later that day. His enlistment record describes him as 5 feet, 4 inches tall, with black hair, black eyes, and a black complexion. His regiment primarily performed post and garrison duty at Lake Providence, Louisiana, until February 1865. They spent the following year on garrison duty in Little Rock, Arkansas, and in Vicksburg. White mustered out on March 20, 1866, in Natchez, Mississippi.
White remained in Natchez after his service, and he married Julia Knight there in 1866. They had no children together, and Julia died sometime before 1911. White suffered from rheumatism and heart disease later in life, and he secured a $12 monthly pension in 1892. The government eventually increased his pension to $30 per month. He died sometime after 1922.