First a part of Dunstable, Massachusetts, then settled as West Hollis, the town was granted in 1769 as Raby. Governor John Wentworth named it after his cousin, 4th Earl of Strafford and Baron of Raby Castle.
The town was renamed in 1798 at the suggestion of a leading citizen originally from Brookline, Massachusetts. By 1859, when the population was 718, there were eight sawmills, one gristmill, and a sash and blind shop. The town was noted for producing lumber, charcoal and casks.
The town received national attention in 1997, when people participating in the traditional ringing of the Congregational Church bell at midnight on the Fourth of July were arrested. Several prominent members of the community were among those arrested, including Road Agent Clarence Farwell and his wife. The incident led to an investigation of the Brookline police department after questions of excessive force were raised following the arrests.
Brookline has several buildings on the National Register of Historic Places.
As of the census of 2000, there were 4,181 people, 1,343 households, and 1,146 families residing in the town. The population density was 211.5 people per square mile (81.7/km²). There were 1,384 housing units at an average density of 70.0 per square mile (27.0/km²). The racial makeup of the town was 97.87% White, 0.14% African American, 0.19% Native American, 0.62% Asian, 0.05% Pacific Islander, 0.22% from other races, and 0.91% from two or more races. Hispanic or Latino of any race were 0.91% of the population.
There were 1,343 households out of which 51.9% had children under the age of 18 living with them, 76.7% were married couples living together, 5.7% had a female householder with no husband present, and 14.6% were non-families. 10.6% of all households were made up of individuals and 3.1% had someone living alone who was 65 years of age or older. The average household size was 3.11 and the average family size was 3.36.
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