The Town of Brookline was originally located in parts of Putney, Athens, and Newfane. The first Settlements were made in 1777 along the valley of Grassy Brook. No political rights were granted until 1794 when the settlers organized and held their first Town Meeting in 1795. At that time, there were no churches or schools and meetings were held in private homes.
Between 1794 and 1824, lands were cleared, roads were laid out and businesses were started. During that time, three stores, two hotels, two blacksmith shops, three sawmills, two grist mills, one tannery and one ashery existed. One doctor and one counselor at law were in practice.
In 1819, part of Newfane lying on the eastern side of the West River was annexed to Brookline. In 1823 Brookline was granted a charter, and in 1824 the Town sent its first representative to the State Legislature.
In 1822, the Round Schoolhouse was built and used as a school until 1929 when it was replaced by the present school building. The Round Schoolhouse served the Town from 1929 to 1989 as a Town Hall for various town functions.
In 1836 the Brookline Baptist Church was erected. It is currently known locally as The Historic Brookline Church.
Mail service from Bellows Falls via Saxtons River to Brookline was started in 1837. At one time the Post Office was located in the present Meehl house.
In November 1927, the bridge to Newfane was washed out in a flood, and in the spring of 1928, the present iron bridge was built. Again, in 1936 and 1938, there were floods causing substantial damage.
Over the years farming has played an important role in Brookline's land use and local economy. Many farms have ceased to operate and at this time in 2013 there is only one produce farm and one stable. Today Brookline serves mostly as a residential community relying on the commerce and industry of surrounding towns.