Having already booked their places in the quarter-final of the competition, there was little at stake for both sides in a game that would only determine who wins Group A.
Despite the minimal consequence of the result, it was Chile who looked like paying little heed to the billing by moving ahead inside three minutes following a fine start.
Bolivia's 3-2 win over Ecuador last time out was their first victory in the Copa America for 18 years, and Mauricio Soria's side looked a little short of incentive in a first half that the host nation dominated.
Alexis Sanchez was thwarted by the post on 19 minutes and on the half-hour mark - both from free kicks - before the Arsenal man was rewarded for his perseverance.
However, they fell further behind 20 minutes later when Chile added a third, as Angelo Henriquez crossed low for Aranguiz to grab his second with a tap in at the back post.
With the game sewn up, Chile continued to attack and scored a fourth through Gary Medel, who latched on to the end of a Valdivia pass and lofted it over the keeper.
Things got worse for Bolivia in the final five minutes as Ronald Raldes sliced the ball into his own net from Henriquez's cross to make it 5-0.