Rochester was settled in 1679 on the lands called "Sippican" by the local Wampanoags, along the coast of Buzzards Bay. (Sippican was the name of the local tribe.) It originally included the lands of Mattapoisett, Marion and parts of Wareham (which was lost when Wareham was founded in 1739). The town was officially incorporated on June 4, 1686 as Rochester, and was renamed for Rochester, England, from which early settlers to the town came. The town originally thrived with the early shipbuilding and whaling trade in Mattapoisett Harbor. However, in 1852 and 1857 the towns of Marion and Mattapoisett, respectively, were separated and incorporated as separate towns, thus landlocking Rochester. Since that time, the town has become mostly rural-residential, with some farms located in town. Rochester is a "Right to Farm" community.

According to the United States Census Bureau, the town has a total area of 36.4 square miles (94 km²), of which 33.9 square miles (88 km²) is land and 2.5 square miles (6.5 km²), or 6.76%, is water. Rochester is located along the western border of Plymouth County, and is bordered by Lakeville and Middleborough to the north, Wareham and Marion to the east, Mattapoisett to the south, and Acushnet and Freetown to the west. The town's localities include Bisbee Corner, East Rochester, North Rochester and Varella Corner. The town is about 10 miles (16 km) northeast of New Bedford, 40 miles (64 km) east of Providence, Rhode Island, and 60 miles (97 km) south of Boston.

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