The area comprising modern-day Smithfield was first settled in 1636 by several British colonists, including John Steere as a farming community and named after Smithfield, London. The area was within the boundaries of Providence until 1731 when Smithfield was incorporated as a separate town. Chief Justice Peleg Arnold lived in early Smithfield, and his 1690 home stands today. There was an active Quaker community in early 18th century Smithfield that extended along the Great Road, from what is today Woonsocket, north into south Uxbridge, Massachusetts. This Quaker community, and its members, became influential in the abolition movement, with members such as Effingham Capron and Abby Kelley Foster, and also gave rise to other Quaker settlements including one at Adams, Massachusetts where Susan B. Anthony was born as an early member. Elizabeth Buffum Chace is a well known person from Smithfield who was influential in both abolition of slavery, and the women's rights movement. In the 19th century several mills were built in the town. In the mid-19th century the towns of North Smithfield, Rhode Island, and Lincoln, Rhode Island, became separate towns. The colonial ghost town of Hanton City is located within the boundaries of present-day Smithfield, but was a completely separate community in the eighteenth century.
Bryant University, a private university with programs in business and the arts and sciences, is located in Smithfield. Smithfield contains several public elementary schools and a public high school, which was ranked 17th out of 52 high schools in Rhode Island in 2006. St. Phillip's School, a private Roman Catholic academy offering education in grades K-8, is situated in Greenville. Mater Ecclesiae College, a Catholic college, is also located in the town in a facility that was formerly the St. Aloysius Orphanage.