Millville was first settled in 1662, and officially incorporated in 1916 by division from Blackstone, Massachusetts (which had itself originally been part of Mendon). This region was originally inhabited by the Nipmuck people.

Millville is in the Blackstone River Valley National Heritage Corridor and has a well-preserved lock which was used on the Blackstone Canal in the early 19th century. It also has a historic Friends Meetinghouse. In the first two decades of the 20th century, baseball great Gabby Hartnett, born in Woonsocket, Rhode Island, grew up in Millville, played youth baseball in the Blackstone Valley League, and played for the Chicago Cubs, beginning in 1922. It has recently been discovered that the town's population in the early 1900s until around 1980 was almost 98% Irish Catholic. A Swedish population evidently settled here, and a local cemetery in Uxbridge was their burial site, Norden cemetery, near the Millville line.

According to the United States Census Bureau, the town has a total area of 5.0 square miles (13 km²), of which 4.9 square miles (13 km²) is land and 0.1 square miles (0.26 km²), or 1.40%, is water.

As of the census of 2000, there were 2,724 people, 923 households, and 719 families residing in the town. The population density was 552.1 people per square mile (213.3/km²). There were 958 housing units at an average density of 194.2 per square mile (75.0/km²). The racial makeup of the town was 97.72% White, 0.77% African American, 0.04% Native American, 0.18% Asian, 0.26% from other races, and 1.03% from two or more races. Hispanic or Latino of any race were 0.62% of the population.

...
Wikipedia