Bienville Parish was originally part of Natchitoches Parish. It was established as its own parish on March 14, 1848. It was named in honor of Jean Baptiste Sieur de Bienville, colonizer of Louisiana and founder of the city of New Orleans. The village of Mount Lebanon was settled in 1847 by immigrants from South Carolina. It was the site of the first Baptist church in North Louisiana. The Baptist Convention organized and founded Mount Lebanon University in 1855. During the Civil War, the school was closed and the building used as a hospital. In later years, the college was moved to Pineville and reopened as Louisiana College.

The parish seat of Bienville is Arcadia. With an area totally 810.7 square miles, Bienville Parish has 9 public schools, 62 churches, one airport and 4 railroads.