Bibb County is a county in the central portion of the U.S. state of Alabama. The county is included in the ARC's definition of Appalachia. As of the 24th decennial 2020 census, its population was 22,293. The county seat is Centreville. The county is named in honor of William W. Bibb, the Governor of Alabama Territory and the first Governor of Alabama. H…Bibb County is a county in the central portion of the U.S. state of Alabama. The county is included in the ARC's definition of Appalachia. As of the 24th decennial 2020 census, its population was 22,293. The county seat is Centreville. The county is named in honor of William W. Bibb, the Governor of Alabama Territory and the first Governor of Alabama. He is also the namesake for Bibb County, Georgia, where he began his political career. It is a "prohibition" or dry county; however, a few towns have become "wet" by allowing the sale of alcoholic beverages: Woodstock, West Blocton, Centreville, and Brent. The Bibb County Courthouse is located in the county seat of Centreville.