The Village of Munnsville is centrally located in the town at the junction of Routes 35 and 40.
Asa Munn opened a mercantile business in the community around 1817.
In 1990 the village received national media attention and interviews by Connie Chung when a local dairy farmer, Delbert Ward, allegedly murdered his brother William Ward by suffocation. Delbert was found not guilty at trial. In 1992 this incident was examined in the documentary Brother's Keeper.
Munnsville became a world renowned racing location for skateboarding because of the Madison County Gravity Festival which began in 2002. Skateboarders from all over North America and Europe descend on the town for the last weekend of July and race their skateboards at speeds up to 95 km/h.
Munnsville was the final home of poet Hayden Carruth.
The former Munnsville depot of the defunct (March 29, 1957) New York, Ontario & Western Railway is now a private residence, occupied by noted NYO&W historian and author John Taibi.
Munnsville is the birthplace of Bill Horr, who won silver and bronze at the Olympics.