Ms. Pilon's postsecondary education began at McMaster University in Hamilton, Ontario. She majored in history, English, and religious and cultural studies. Immediately after receiving her Bachelor of Arts with honors in 1989, she took advantage of the school's international teacher program to instruct students in Israel and Egypt for a year. Upon her return to Canada, Ms. Pilon obtained a Bachelor of Education from York University with a certification to teach in Ontario.
Our Lady of the Assumption Elementary School in New Lowell offered Angelina Pilon her first full-time teaching position in Canada. She taught there for four years, followed by three years at Our Lady of Grace Elementary School in Angus. Further positions as a primary, junior, and intermediate instructor followed, as well as an adjunct professor post at York University.
In anticipation of a career in school administration, Angelina Pilon completed a principal's qualification program in 2003 and accepted the position of Vice Principal at Pine River Elementary School in Angus. She earned her Master of Education from Charles Sturt University in 2008 and qualified for an Ontario Supervisory Officers Certification the following year. Throughout this period, from 2003 to 2009, Ms. Pilon held full-time administrative positions, as Principal of Brechin Public School and Supervisor and Instructor for the Principal's Qualification Programme at Nipissing University. She also served as supervisor for various summer literacy and mathematics camps for fourth- through ninth-graders in Simcoe County school district in 2009.
Angelina Pilon has continued to add to her skills by taking professional courses offered by the Ontario Ministry of Education. These have included training in social justice and diversity in public schools, as well as 21st-century education methods and technology.