The game got off to a tough start after both teams were locked with a try each at half time.
Samoa however converted their try from Tanu Levaea, which gave them a 7-5 lead at half time.
The try from Chile was scored by Ernesto Tchimino.
Samoa dominated the entire second half with a total of four tries from Tuna Tuitama, Paul Eti Slater, Owen Niue and Vaovasa Afa Sua.
Samoa will play New Zealand in their last pool game at 1:30pm (Samoa Time).