Two goals for Charles Aranguiz, one each for Alexis Sanchez and Gary Medel and an own goal from Ronald Raldes put Chile's campaign back on track after Vidal's arrest following a high-speed crash threatened to derail their tournament.
The win ensured Chile finished top of Group A and gives them a last eight meeting next Wednesday against one of the two best third-placed teams, most likely either Uruguay or Paraguay.
Bolivia, who had been guaranteed a place in the knockout rounds for the first time in 18 years after Ecuador defeated Mexico in Friday's early game, were never in contention against La Roja.
The Chileans swept into an early lead after only three minutes with a well-worked goal from Aranguiz.
Inter Milan defender Medel pumped a long ball forward, and Eduardo Vargas knocked down into the path of Aranguiz, who drilled a low shot beyond Bolivia goalkeeper Romel Quinonez.
Buoyed by the early goal, Chile went for the kill and threatened to run riot over a Bolivian side who seemed to freeze.
Sanchez twice saw free-kicks rattle against the woodwork as Chile pummeled Bolivia's goal but somehow they managed to survive the onslaught.
Yet on 37 minutes their resistance finally broke after a superb move started and finished by Sanchez.
Picking up the ball wide on the left, Sanchez cut in and burst clear of the Bolivian cover before releasing Jorge Valdivia down the right.
The Palmeiras playmaker returned the favour to pick out Sanchez as the midfielder continued his run into the penalty area, stooping low to direct an angled header into the far corner past Quinonez.
Chile's attacking momentum was interrupted after half-time, when coach Jorge Sampaoli withdrew both Vidal and Sanchez in a double substitution, but the hosts remained firmly in control.
Aranguiz put the game beyond Bolivia's reach in the 66th minute, grabbing his second after latching on to a low cross from Angelo Henriquez.
Medel made it 4-0 10 minutes from time, playing a one-two with Valdivia, controlling on his chest and then lifting a chip over Quinonez for a superb individual effort.
A miserable night for Bolivia was compounded when captain Raldes inadvertently chipped Quinonez for an own goal to make it 5-0 after Henriquez's cross.