Born in County Kildare, Ireland, Whiteley immigrated to the United States in 1836 with his parents, who settled in Georgia. He received private instruction in elementary education. He engaged in manufacturing. He studied law and was admitted to the bar in 1860, commencing practice in Bainbridge, Georgia. Whiteley opposed secession, but after the adoption of the ordinance entered the Confederate States Army and served throughout the Civil War, attaining the rank of major. He served as member of the State constitutional convention in 1867.