Wales was first settled in 1726 and was officially incorporated on August 23, 1775, as South Brimfield, a name it kept until February 20, 1828. The town was renamed after James Lawrence Wales, a local benefactor. Initial settlers included John Bullen, and Samuel and Dorothy Munger. The next generation of Mungers became prominent in the town. Samuel (Jr.) served as a selectman and was deacon of the Baptist Church for many years. Nathaniel was one of 12 men of the district appointed as a "court of Justice and Honor to determine all controversies that may hereafter arise in said District," and was also a deacon of the Baptist Church. The "Meadow District" of Wales was originally known as "Munger's Meadow" and includes graves of early pioneers.

According to the United States Census Bureau, the town has a total area of 16.0 square miles (41 km²), of which 15.8 square miles (41 km²) is land and 0.2 square miles (1 km²) (1.32%) is water. Wales is bounded on the west by Monson; on the south by Stafford, Connecticut and Union, Connecticut; on the east by Holland; and on the north by Brimfield.

Wales Elementary School, serving grades K-6, has its own school committee, part of School Union 61. Wales students attend Tantasqua Regional Junior High School (grades 7-8) and Tantasqua Regional High School in Sturbridge. Union 61 and the Tantasqua district share administrators, including the superintendent, and both include Brimfield, Brookfield, Holland, Sturbridge and Wales.

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