Born at Singleton Abbey, Swansea, Henry was the eldest son of industrialist and MP John Henry Vivian and his wife Sarah, daughter of Arthur Jones, of Reigate. His younger brothers were Arthur Vivian (who would become an industrialist and MP), Richard Glynn Vivian (afterwards an art collector and philanthropist) and Graham Vivian. His uncle was Richard Hussey Vivian, first baron Vivian. He was educated at Eton and studied metallurgy in Germany and France from 1838 before entering Trinity College, Cambridge in 1839. After two years he became manager of the Liverpool branch of the copper-smelting business founded by his grandfather, Vivian & Sons.
Three years later he became a partner of the firm before coming to Swansea to manage the Hafod Works during the last ten years of his father’s life (1845–1855). He developed a range of by-products from copper-smelting and diversified into other metallurgical activities
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