Colonization of the place began at the end of the 19th century, when Henri-Joseph Mussely (a Belgian Catholic priest) arrived there, along with about 20 Belgian families. They founded the parish of Saint-Alphonse-de-Liguori in 1891, named after Alphonsus Liguori since Mussely was a Redemptorist. The place was originally known as La Petite-Belgique (French for "Little Belgium"), but the Belgian families did not remain long due to the harsh climate and short growing season, replaced by people from around Chaleur Bay.[1]
In 1901, its post office opened under the name Saint-Alphonse-de-Caplan, referring to the parish name and its proximity to Caplan. The following year, the Municipality of Musselyville was created out of territory ceded by Township of New Richmond and the Parish Municipality of Saint-Bonaventure de Hamilton.[1][4]
On October 24, 1953, the municipality changed its name from Musselyville to Saint-Alphonse.[1][4]
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