Vallieres was in a lead group with New Zealand’s Niamh Fisher-Black and Spanish veteran Mavi Garcia near the end of the 164km slog on a hilly circuit when she burst clear.
Powering up the ascent towards the finish line, the 24-year-old stayed clear of Fisher-Black, who came home second with García third.
The championships, the first to be held in Africa, conclude on Sunday with the elite men’s road race.
The championships, the first to be held in Africa, conclude on Sunday with the elite