Originally part of Voluntown, this northern section separated and obtained town privileges from the CT. Assembly May 1794.

Sterling was given its name in honor of a resident, Dr. John Sterling. He promised the town a Library in return for this honor. The Dr. did not follow through on his commitment, but the town eventually obtained a library by soliciting private donations.

The first town meeting was held June 9, 1794, at the Dixon home on Sterling Hill.

The first post office was established as Sterling on Oct. 1, 1809.

The American Manufacturing Company, also known as Potter's factory, was the first cotton mill in Sterling, @1800. It was situated on the Quandock River. The Sterling Manufacturing Company located in Sterling @1808, and was located on the Moosup River.

Local Industrialist William Pike pioneered in using chlorine as a bleaching agent for cloth and also established for the use of the dyer distilleries or sap works that would extract the first pyroligneous acid made in this country. His son James discovered a process of coloring with a fast black that was superior to any then in use. With the advent of the first railroad in 1854, which connected Providence with Hartford, distribution of materials became much easier and contributed to the economic base of Sterling. Oneco, a village within the town of Sterling, was named after Owaneco, son of the Mohegan Indian sachem Uncas, who claimed ownership of large tracts of eastern CT. land in the early colonial days.

About 1820 Henry Sabin built a cotton mill in Sterling.

In the 1850's quarrying began in Sterling, and is still an active industry today.