Samoa came from behind to score four tries and secured a 43-10 victory, and a bonus point, to go top of Pool D.
They endured a slow start before outclassing the tournament debutants with backline craft and forward power to get their campaign off to a winning start at Stade de Bordeaux on Saturday.
Samoa delighted the massed ranks of their exuberant fans by scoring the opening try of the match through prop Matias Dittus and Samoa needed the place-kicking of Christian Leali'ifano to creep ahead towards the end of the first half.
Tries from fullback Duncan Paia'aua and scrumhalf Jonathan Taumateine immediately before and after halftime gave the Pacific islanders some breathing room and two tries from rolling mauls secured the bonus point.
Despite backing up from their loss to Japan last Sunday and having two players sin-binned, the Chileans continued to fight and had the better of a scrappy final quarter until Samoa's reserve hooker Sama Malolo scored his second try late on.
Additional reporting by Reuters.