George Alley was born in Charlottetown, Prince Edward Island on 22 January 1844, son of architect Thomas Charles Alley and Anne McKay. George Alley married in 1871 Mary Trew Blatch, (1843-1897). George and Mary (Blatch) Alley had the following children: Gordon Thomas Alley, MD, (1874-1925), Evelyn Trew (1873-1938), Helen Blanche (1871-1889), and George Cyril (1876-1920).

George Alley attended Central Academy, in Charlottetown. He studied law, and was admitted to the bar in 1865. In 1868, Alley joined with Louis H. Davis to form the law firm Alley and Davis. Alley was appointed judge of the Queens County Court on 18 July 1874, possibly the youngest judge ever appointed in Canada. Published reports indicate that Judge Alley had been collecting historical and archival information for many years with the intention of writing a history of the early settlement of Prince Edward Island. This was never achieved due to his untimely death. Judge Alley was a member of the Numismatic and Antiquarian Societies of Canada and was an Executive Committee member and Corresponding Secretary of the Historical Society of Prince Edward Island which was in existence from September 1881 through September 1882. Alley was involved in the militia as a Lieutenant in the PEI Lighthorse. Alley was one of the founding members of the Historical Society of Prince Edward Island whose purpose was the collection and preservation of historical documents pertaining to PEI which were in private possession. Unfortunately, after several poorly attended meetings and without government support for the endeavour, the Society folded and its collection was offered for sale to its members. Judge George Alley died 6 May 1899.