He left college in 1855, on his father's death, to manage the family's copper smelting and rolling works and colliery at Port Talbot.

He was Colonel commanding the South Wales Border Volunteer Infantry Brigade from 1895 to 1902, was appointed a Knight Commander of the Order of the Bath (KCB) in the 1902 Coronation Honours list published on 26 June 1902,[7][8] and invested as such by King Edward VII at Buckingham Palace on 24 October 1902.

He published Wanderings in the Western Land (1879),[10] describing his travels in North America, starting 14 August 1877 in St Johns, Newfoundland.

[11] Vivian married firstly, 3 March 1867, Lady Augusta Emily Wyndham-Quin, daughter of 3rd Earl of Dunraven.

Vivian sold his residence Glendorgal, near Newquay on 11 December 1882 and bought the Bosahan estate, near Helston in the same year, living there from 1885 until he died in 1926, aged 92.