Williams was born in 1813 in England, to Burton Williams, a colonist from Trinidad, and his wife Jane; he was the couple's sixth son. In November 1833, after completing his education, Williams was called to the bar of the Inner Temple where he practised as a barrister. Williams was born to a slaveholding family. His father owned some 450 slaves, in Trinidad in the 1820s. Edward was later a trustee to his insane brother, who was compensated on the emancipation of slavery in the 1830s. Williams married Jessie Gibbon, a minister's daughter, on 13 March 1841.
Williams decided to move to Australia, arriving with his wife in the Port Phillip District on 13 February 1842, where he initially planned to become a squatter. However, he soon abandoned this idea and joined the Melbourne bar on 30 March 1842, making his first court appearance the following month where he performed well. In the 1840s, although there were a few other members, the Melbourne bar essentially consisted of Redmond Barry and William Stawell, along with Williams, Robert Pohlman and Archibald Cunninghame. Barry, Stawell, Williams, Pohlman, James Croke and Edward Brewster, all with either Irish or English educational and legal backgrounds, were something of "an informal Senior Common Room" in Melbourne in the 1840s, "dining and socialising together and generally supportive of their own brand of legal manners." In May 1844 Williams was appointed to the Bourke District local council. He contributed to efforts to establish the Melbourne Hospital from 1845, and in 1847 was a member of its first management committee. In 1848, Williams represented William Kerr, the proprietor of The Argus, in defence of a libel case brought by the mayor of MelbourneHenry Moor. Kerr lost the case, and the damages he had to pay pushed him into insolvency, forcing him to sell The Argus. Williams later represented Edward Wilson and James Johnston against another libel suit brought by Moor. Moor won this case too, but was awarded only token damages of one farthing. In both cases, Moor was represented by William Stawell. Williams was appointed the commissioner of insolvent estates on 1 April 1851. Later that year he intended to stand in the first election for the Legislative Council of Victoria, but when made Commissioner of the Court of Requests in late July 1851, he withdrew from the election. He was also appointed chairman of the Court of Quarter Sessions in January 1852. Williams would become a member of the Legislative Council from 13 April 1852, when he succeeded Redmond Barry as Solicitor-General of Victoria, after Barry was appointed a judge of the Supreme Court of Victoria. Williams was Solicitor-General for barely three months, however, since he was himself made a judge of the Supreme Court on 21 July 1852, bringing the Court to its full complement of three judges. As a judge, Williams was recognised for his diligent and efficient work at the circuit sittings of the Supreme Court in various parts of the colony. Before the penetration of railways into the interior, many of the journeys to the circuit sittings were made on horseback. Only limited amounts of time were available for each of the circuit destinations, and Williams would often hold sittings until the early hours of the morning in order to maintain the busy schedule of cases. Williams took a two-year leave of absence in England, beginning in April 1859. In 1872, the youngest of Williams' two daughters was killed in a mountaineering accident in Switzerland, when she fell from a cliff. Crushed by this loss, and suffering from poor health, Williams was advised by his doctors to leave the bench, and he resigned from the Court in April 1874. He left Australia with his family on 28 May of that year, returning to England. Williams retired to the city ofBath; knighted on 28 May 1878; He died on 30 April 1880, survived by his wife Miss Jessie Gibbon, a daughter and two sons, the younger of whom was Hartley Williams.
