Léo Roland Piquette was born on May 22, 1946, the fifth son of Roland and Zéa Piquette, descendants of the founders of Plamondon, Alberta. He married Valerie Coté, daughter of Evangeliste and Léa Coté, on May 30, 1969 and together had three children, Colin, Michelle and Andrea. He had three more children from his second marriage with Mary Snyder in July 1987: Dominic, Julien and Carroll.

Having completed his Bachelor of Education degree at the University of Alberta in 1970, Léo Piquette returned to Plamondon to start teaching. He was appointed principal of Caslan Elementary School in 1970 and was principal of Vermilion Elementary School from 1972 to 1975. In 1975 Léo and Valerie moved to Edmonton where Valerie returned to studies at the university and he taught for one year at Belgravia Elementary School. In 1976 he was vice-principal of Satoo Elementary School and in 1977 he was principal of J.E. La Pointe School in Beaumont. From 1978 to 1982 Léo Piquette was in the publishing business. In 1982 he returned with his family on their farm in Plamondon where he started to teach at Plamondon School. He soon became involved in community activities as president of the Association canadienne-française de l'Alberta (ACFA), regionale de Plamondon. In 1984 he helped the Alberta New Democrats to organize the new Lac La Biche provincial constituency. He ran in the next election and won as NDP candidate in the provincial constituency of Athabasca/Lac La Biche in May 1986.

On April 7, 1987 Léo Piquette posed a question in French in the Alberta Legislature, earning an 'En anglais, s'il vous plait!' from David Carter, then Speaker of the Legislative Assembly. The 'Piquette Affair' story was on the headlines nationwide and sparked a constitutional debate that would go all the way to the Supreme Court of Canada. This incident incited nationwide discussion regarding the role of French in the Canadian political arena.

Léo Piquette was defeated in the 1989 elections and decided to change the course of his life, getting involved in business. In 1990 he took ownership of the Plamondon Co-operators Insurance Agency under the name of Piquette Agencies Ltd. He also became chair of the Conseil scolaire Centre-Est and of the Fédération des conseils scolaires francophones, administrator of the Réseau de développement économique et d'employabilité (RDEE) in Western Canada, and president of the Economic Chamber of Alberta.