The World Cup host gave a sterling display of its attacking credentials with a high octane performance to see to its South American rival, with Neymar shining again.
The 2014 World Cup host extended its unbeaten run against Chile to 12 matches, dating back to Aug. 2000, thanks to Robinho's 79th-minute winner.
Eduardo Vargas had cancelled out Hulk's first-half opener with a tremendous strike at the Rogers Centre in Toronto, but Robinho's header saw Brazil continue its fine form as the side made it six matches without a loss.
Neymar, who was targeted by Honduras in the 5-0 win on Saturday, fired the first shot at goal, putting his effort from an angle just outside the area well wide.
Chile made a slow start and was punished for an error in the 14th minute when Hulk opened the scoring.
Marcos Gonzalez's sloppy pass out of defense went straight to Oscar and the Chelsea midfielder slipped Hulk through on the left side of the area. The Zenit man unleashed a powerful left-footed strike into the bottom corner, with Claudio Bravo unable to keep it out.
Chile began to settle and put Brazil under pressure after going behind, but struggled to create clear-cut chances. Vargas threatened for Chile just four minutes into the second half, curling a 20-yard shot wide.
Brazil went close in the 51st minute when a Maxwell cross from the left was cleared by Gonzalez as Paulinho lurked at the back post.
The Confederations Cup champion looked most dangerous on the counterattack and threatened again five minutes later when Neymar fed through Robinho, whose shot was saved. From the resultant corner, Hulk picked up the scraps at the edge of the area and hit the post with a powerful strike.
Chile surprisingly hit back through Vargas in the 71st minute. Substitute Jean Beausejour headed a Bravo goal kick to Vargas, who took a touch before finishing into the bottom corner from 20 yards.
Just two minutes later and Brazil thought it was back in front. Neymar flicked in a cross, but the Barcelona attacker had come back from an offside position and the goal was ruled out.
But the Brazilians only had to wait until the 79th minute to score what proved to be the winner thanks to Robinho. Neymar concluded his dazzling run with a pass out right to Maicon, whose first-time cross picked out an unmarked Robinho to head in.
It could have been three through Neymar but he was unable to complete an excellent display with a goal as Bravo denied him.