Waterville is located in a small, low-lying valley between steep hills and mountains, and is situated in the northwestern section of Lamoille County. It is bound by Bakersfield on the north and west, Cambridge on the south and west Belvidere and Johnson on the east and Fletcher on the west. The town has a Planning Commission and a town plan. It has no zoning or subdivision regulations. VT Route 109 bisects the town and serves as the major route connecting Waterville to Eden and Route 100 to the northeast and Cambridge and Route 108 to the west.

The main village center is located on Route 109. The population of Waterville has grown to 673 in 2010.