The highway runs 14.139 miles (22.755 km) from the Massachusetts state line north to NH 12 in Keene.

NH 32 connects the southern Cheshire County towns of Richmond and Swanzey with Keene and Athol, Massachusetts.

NH 32 begins at the Massachusetts state line in the town of Richmond.

The highway continues south as Massachusetts Route 32 (Richmond-Athol Road), which heads through Royalston toward Athol.

The highway continues north as Old Homestead Highway, which enters the valley of the South Branch of the Ashuelot River as the route enters the town of Swanzey.