Mathews trained and qualified as an architect before becoming a painter, as a pupil of the late Eustace Frere and at the Architectural Association School in London. He went to Paris in 1923 and studied painting there at Académie Moderne under Othon Friesz and Fernand Léger. He lived and painted principally in France between the two World Wars.

He was President of the National Society of Painters, Sculptors and Engravers.