Samuel Willard treated many smallpox victims in South Uxbridge and Glocester (Burrillville), and he had the scars to prove it.

[4] The Nipmuc word for snake was rendered "askug" by Roger Williams in his A Key Into the Language of America, and "askoog" by the Reverend John Eliot in his Algonquian translation of the Bible.

Burrillville's principal village, Pascoag, named after the stream upon which it is located, probably derives from this Algonquian root.

It was incorporated as an independent municipality on November 17, 1806, when the Rhode Island General Assembly authorized the residents of then North Glocester to elect its own officers.

The town was named for 19th century United States senator James Burrill, Jr. who was then the Rhode Island Attorney General.

In the Rhode Island Senate, Burrillville is a part of the 23rd District and is currently represented by Republican Jessica De La Cruz.

In presidential elections, Burrillville has traditionally leaned Democratic; however, in 2016, Donald Trump became the first Republican to win the town in over three decades when he defeated former U.S. Secretary of State Hillary Clinton by approximately 22 points.

Burrillville was also one of seven towns in Rhode Island where independent candidate Ross Perot finished in second place during the 1992 presidential election.