 Mathews went to Sydney in 1893, and became secretary of the Wooloomooloo branch of the Labor Party in the same year; he also organised for the Tailors' Union while in Sydney.Mathews returned to Melbourne in 1898, and worked for the Collins St firm of Haig Bros. before going into business for himself; he was operating a tailoring business in South Melbourne opposite the South Melbourne Post Office at the time of his election.Prior to his election, Mathews also spent six years as the secretary of the South Melbourne branch of the Labor Party, remained involved in the Tailors' Union, and had made two unsuccessful candidacies for the City of South Melbourne council.