Much of the build-up to the match focused on midfielder Arturo Vidal's arrest for crashing his Ferrari while driving under the influence of alcohol. However, Chile put the incident behind them and clinched the top spot in Group A thanks to Charles Aranguiz's brace. Alexis Sanchez and Gary Medel added to the scoreline before an unfortunate own-goal from Ronald Raldes sealed the win for Chile.
Aranguiz opened the scoring for Chile in the third minute after latching onto a knockdown from Eduardo Vargas following a long ball from Gary Medel.
Chile nearly doubled their lead in the 19th minute, but Sanchez's free-kick hit the side of the post. The Arsenal man came close once more 12 minutes later, with a free-kick ricocheting off the crossbar.
It was third time lucky for Sanchez in the 37th minute. The Chilean number seven pounced on a loose ball after Bolivia lost possession on the halfway line, driving towards the area before laying the ball off for Jorge Valdivia who crossed the ball into the box, with Sanchez executing a perfect diving header to put the ball beyond Bolivia goalkeeper Romel Quinonez.
Vargas had an opportunity to make it 3-0 to Chile in the 41st minute, but his attempt on goal went wide.
With a 2-0 lead at half-time, Sanchez and Vidal were substituted, and while their absence did take some of the intensity out of the match, Chile still continued to dominate.
Aranguiz scored his second goal of the match in the 66th minute when he slotted the ball into the back of the net following a cross from substitute Angelo Henriquez.
Medal made it 4-0 in the 80th minute when he chipped the ball over Quinonez in delightful fashion.
As if things couldn't get any worse for Bolivia, defender Raldes scored an own-goal when trying to clear the ball in the 86th minute.
Chile finished atop the Group A standings with seven points after having won two games and drawn one, while Bolivia will also advance to the next round after Ecuador beat Mexico 2-1 earlier in the day.