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The town of Washington's namesake is George Washington. Some of the original settlers of the area were Colonel Andrew Ellicott, Joseph Calvit and John Foster.
The seat of the territorial legislature was moved from Natchez to Washington on February 1, 1802, and remained there until statehood in 1817.
The Mississippi statehood convention of 1817 met in the Methodist Meeting House at Washington, which was later purchased in 1830 by Jefferson College.
Fort Dearborn, located at Washington, was for a time the largest military installation then extant in the United States, with over two thousand soldiers stationed there, including such notables as future General Winfield Scott.
Washington is the location of Jefferson College, now known as Historic Jefferson College, which is a state historic park and museum operated by the Mississippi Department of Archives and History. The college was created by an act of the first General Assembly of the Mississippi Territory in 1802 and was named in honor of Thomas Jefferson, then-president of the United States. Although chartered in 1802, it did not become a fully functional school until 1811. It continued, more or less, uninterrupted in this capacity (but for a few brief, temporary closures, due to war, fire, remodeling and the like) for the next 153 years, finally closing its doors for good in 1964. In contradistinction to its nearby sister school, the Elizabeth Female Academy, which for most of its history was a degree-conferring college, Jefferson College was for nearly the entirety of its existence an all-male, college-preparatory academy, then (as Jefferson Military College), a military-style boarding school.
Elizabeth Female Academy, considered to be the first true women's college in the state (in spite of its name), was established at Washington in 1818, closing in 1845.
Clear Creek Baptist Church, erected in 1825 and one of the oldest churches in Mississippi, is located in Washington, along with Washington Methodist Church.
In 1879, the Jesse James gang robbed two stores in Washington and in Fayette in Jefferson County, Mississippi. The gang absconded with $2,000 cash in the second robbery and took shelter in abandoned cabins on the Kemp Plantation south of St. Joseph, Louisiana. The posse attacked and killed two of the outlaws but failed to capture the entire gang. Jesse James would live another three years until his demise in, coincidentally, another St. Joseph in northwestern Missouri.
Former Mississippi Governor Bill Allain was born in Washington on February 14, 1928. In 1788, the first native-born Mississippi governor, Gerard Brandon, was born at his family's plantation, Selma, just outside Washington.