It runs from the Willimantic section of the town of Windham to the Rhode Island state line in Sterling.

It also overlaps Route 97 for 0.68 miles (1.09 km) from the eastern section of town to the center of it.

Immediately after crossing the Quinebaug River into the town of Plainfield, Route 14 turns left onto Black Hill Road while Route 14A continues straight as Canterbury Road.

East of I-395, Route 14 heads into the village of Moosup where the road uses a pair of one-way streets.

Sterling Road goes through the town center and meets with the east end of Route 14A at the Rhode Island state line.

A 4.4-mile (7.1 km) section between Windham and Scotland is a designated state scenic road, running through mostly rural areas.

It runs south of Route 14 between Canterbury center and the Rhode Island state line.