The 2014 FIFA World Cup hosts extended their unbeaten run against Chile to 12 matches, dating back to August 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 their fine form as they made it six matches without a loss.
Neymar, who was targeted by Honduras in Brazil's 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 were punished for an error on 14 minutes when Hulk opened the scoring.
Marcos Gonzalez's sloppy pass out of defence went straight to Oscar and the Chelsea midfielder slipped Hulk through on the left side of the area.
Hulk 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 on 51 minutes when a Maxwell cross from the left was cleared by Gonzalez as Paulinho lurked at the back post.
The Confederations Cup champions looked most dangerous on the counter-attack 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 on 71 minutes.
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 they were 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 they 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.
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