According to the U.S. Census Bureau, Centreville has a total area of 9.6 square miles (24.9 km2), of which 9.5 square miles (24.5 km2) are land and 0.15 square miles (0.4 km2), or 1.52%, is water.
The Cahaba River falls near Centreville, which made the town a strategic location for transportation through the region. The first post office in Bibb County was established in Centreville in 1821. Sarah Willis Chotard obtained a patent for land in this area in 1823 and began moving squatters off the land and laid out a plot for the new town of Centreville.
In 1829, Centreville became the permanent seat for Bibb County after several years of debate and different locations of the county courthouse, and the town was incorporated in 1832. Centreville's historic district is listed on the National Register of Historic Places.
Cahawba Christian Academy is a private school serving grades pre-K to 12.