She died in 1889 and in February 1896 he married Annie Dudgeon, née Samuel, a widow with three children.

[1][2] Wynne won the seat of Balaclava at the 1906 elections in the Australian House of Representatives as an Independent Protectionist.

He joined the Fusion government and served as Postmaster-General in the Cook Ministry from June 1913 to its fall in September 1914, but he did not contest the 1914 elections, apparently because he could not reorganise his department to run on efficient business principles.

[1] Wynne returned to Victorian politics in 1917, winning the state seat of St Kilda and was Attorney-General, Solicitor-General, Minister of Railways and a Vice-President of the Board of Land and Works from November 1917 to March 1918 in Sir John Bowser's government.

[1] A supporter of the war effort, in 1917 Wynne offered £500 to the first member of the proposed Sportsman's Battalion to win the Victoria Cross.