Midfielder Arturo Vidal was brought down in the box by Miller Bolanos in the second half and picked himself up to convert the penalty for Chile.
Former QPR man Eduardo Vargas netted the second, calmly slotting home, as Matias Fernandez was sent off late on.
Ecuador’s best chance fell to West Ham striker Enner Valencia, who struck the crossbar with a close-range header.
Chile have never won the competition in its 99-year history, coming runners-up on four occasions, the last being in 1987.
And having reached the last-16 of the 2014 World Cup, the Chileans are third favourites behind Argentina and Brazil to lift the trophy this year.
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