Littleton Washington was born in Washington D.C. on November 3, 1825, the son of Lund Washington, whose forebears were cousins of the family of the first president. He enrolled with the class of 1845 at Dickinson College in Carlisle, Pennsylvania and, while there, was an active student, gaining election to the Belles Lettres Society. He was forced, though, to withdraw from the College due to family financial difficulties. He found gainful employment instead as a clerk in the U.S. Treasury.
Washington became a freelance journalist and then took the opportunity offered in a job as assistant collector in the United States Customs House in San Francisco, California, traveling by ship via Panama. He landed in the city at the time of the vigilante violence of 1856 and actively stood with the legal city government against the mob violence designed to rid the city of law breakers. With Buchanan's election, his position went to another and he returned to Washington, this time overland by way of Mexico, experiencing sundry adventures along the unruly and dangerous route. Back in the capitol, he drifted somewhat, fighting the occasional duel and moving on the fringes of government. He supported the hard-line Democrats and, when the split came, he followed his states' rights leanings, at one point helping to organize a pro-southern group called the "National Volunteers." When hostilities commenced in April 1861, he left Washington for Richmond.
Washington served for a time with a commission as a quartermaster in the Confederate Army, seeing action at the first battle of Bull Run before resigning. He served as editor of the Richmond Examiner and then, in 1861, entered the Confederate State Department as the personal secretary of the Secretary of State R. M. T. Hunter, a pre-war acquaintance. When Judah Benjamin took over from Hunter the following year, Washington remained in the department and became a vital part of the tiny department. He did see action once more during the war when, in late February and early March 1864, Union General Kilpatrick, together with a cavalry force under Colonel Ulric Dahlgren, attempted to raid Richmond, release the prisoners at Libby Prison, and capture Jefferson Davis. Washington joined a hastily raised "department clerks battalion" and helped defend the city from the failed raid. While at the State Department, rumors connected him to the Confederate spy networks, perhaps knowing fellow Dickinsonians, David Cloud and Thomas Conrad, then active in the service. Following the war, he returned to work as a journalist, covering the trial of Andersonville Prison commander Captain Heinrich Wirz in the autumn of 1865 for a Virginia newspaper. He also became active in southern veterans associations.
Washington never married. He died in the capital city on November 4, 1902 and is buried in the Congressional Cemetery there. He was seventy-seven years and a day old.