Route 32 begins near Interstate 95 (about 0.5-mile (0.80 km) south of the road crossing as a continuation of Water Street).

It then becomes a mostly two-lane surface road with the exception of the overlap with Route 2 in Norwich.

It goes through the following towns: New London, Waterford, Montville, Norwich, Franklin, Lebanon (0.11 miles (0.18 km) only), Windham, Mansfield, Willington, Tolland (0.10 miles (0.16 km) only), Ellington, and Stafford.

Route 32 between Norwich and New London was laid out in 1670 and remained little more than an Indian trail for more than a century [citation needed].

The modern alignment in Stafford was known as State Highway 334 in the 1920s before being reassigned to Route 32.