The village was named in 1878 after the Green Valley Hotel established in the 1840s by Mary McDonald. During these early days, it was a popular spot just south of Green Valley northeast of the Beaudette River. Travellers between Hawkesbury and Lancaster would stop here for a rest and for a drink. The development of Green Valley gained momentum in 1887 when the Canadian Pacific Railway crossed Highway 34. This would link Green Valley to Apple Hill and eventually Toronto and Montréal.
In 1938 Léo Lajoie built the Green Valley Pavilion which drew crowds from everywhere. The hall became a church in 1956. In the ‘30s Wilfrid Ménard moved into the village with Ménard Construction (now Cruickshank) and Jos Vaillancourt built a large feed mill near the CPR tracks which later burned in December, 1966.