Shaw-Levevre was the son of Charles Shaw-Lefevre by his wife Helen, daughter of John Lefevre. Charles Shaw-Lefevre, 1st Viscount Eversley, was his elder brother. He was educated at Trinity College, Cambridge, where he was Senior Wrangler in 1818, and was called to the Bar, Inner Temple. He was returned to Parliament for Petersfield in December 1832, but was unseated on petition in March 1833. He served under Lord Grey as Under-Secretary of State for War and the Colonies in 1834. The latter year Shaw-Lefevre was appointed a Poor Law Commissioner after the passing of the Poor Law Amendment Act, which he remained until 1841. Between 1856 and 1875 he served as Clerk of the Parliaments. He also helped found the University of London and served as its Vice-Chancellor for many years. He was made a KCB for his public services.
Shaw-Lefevre married Rachel Emily, daughter of Ichabod Wright, in 1824. They had one son, George, who became a prominent politician and was ennobled as Baron Eversley, and five daughters. Shaw-Lefevre died in August 1879, aged 82. His wife lived for 6 more years before dying in February 1885.