William H. Durfee was born around 1833 in Holliston, Massachusetts, to Rufus and Esther Durfee. His father was a bootmaker. He grew up and attended school in Holliston before beginning work as a bootmaker. He married Elizabeth Evans around 1854, and they had at least three children: George, born around 1856; Lionel, born around 1861; and Emma, born around 1866.
He enlisted in the Union army on November 26, 1861, and he mustered in as a corporal in Company H of the 1st Rhode Island Cavalry on December 2, 1861. The regiment took part in the Second Battle of Manassas and the Battle of Chancellorsville. Confederate forces captured him near Beverly Ford, Virginia, on June 9, 1863, but he was eventually exchanged. He was promoted to quartermaster sergeant, and he mustered out on August 3, 1865.
He returned to Holliston after the war and resumed his work as a bootmaker. He applied for a federal pension in November 1890 and eventually secured one. By 1900, he was working as a night watchman. He died of chronic interstitial nephritis in Holliston on February 20, 1904.