He was president of Centenary College of Louisiana from 1849 to 1853 and subsequently president of La Grange College near Leighton, Alabama, an esteemed early Methodist institution.
He also served as president of Centenary Institute in Summerfield, Alabama for a short time.
Rivers was instrumental in relocating the fiscally troubled La Grange to nearby Florence in 1855, where it retained its Methodist affiliation and was known variously as Florence Wesleyan and Wesleyan College.
Briefly prosperous, college failed during the Civil War after Rivers himself had departed.
He was the author of several important treatises, including Elements of Moral Philosophy, a college text used throughout the south in the 1850s justifying slavery on theological grounds.