Ranked 89 in the world, Roger-Vasselin was the top seed in the qualifying competition and beat Ward 6-3 6-3 to claim the victory.
Ward, who upset Andrey Golubev to set up the qualifying decider, had raced out to a 3-0 lead in the first set but his French opponent quickly took control of proceedings.
Roger-Vasselin was dominant on his serve for the rest of the match, rattling off six games in a row to take the first set before a solitary break sealed the victory in the second.
Ward's defeat means that Andy Murray will be the sole Briton in the male event.
Daniel Evans also entered qualification but lost to 12th seed Bjorn Phau on Monday.