George Booley was born in Kew, Victoria and enlisted in the Australian Imperial Force at Melbourne on 19 August 1914. Prior to the outbreak of the First World War, Booley worked as a farmer in the Banyan area. He was assigned to the 5th Infantry Battalion and departed Melbourne on 21 October 1914 aboard HMAT Orvieto. After a short time in Egypt, Booley was transferred to Gallipoli where he served as part of the second wave of attacks on 25 April 1915. During the landing, he was wounded and invalided to Mudros and then Helipolis, Egypt.

After recovering from his wounds, Booley joined the 5th Infantry Battalion in France. In July 1916 he received a recommendation for a Mention in Orders as part of signals group that risked their lives to keep communications open during heavy shelling at Pozieres. By 1917, Booley had been commissioned as a lance corporal and spent time in England on leave. After returning to the front in early 1918, he was struck down by illness and remained in hospital until September. George Booley briefly returned to the front before leaving to return to Australia on 8 October 1918.