Lucas Paqueta was on target for the holders just minutes after coming on as La Roja upped the ante after Gabriel Jesus was sent off.
In the first-half it was all Seleccao who created the better chances, but couldn't find a way past Claudio Bravo as Roberto Firmino, Danilo and Gabriel Jesus were all guilty of missing crucial opportunities.
Martin Lasarte's side looked dangerous going forward without ever testing Alisson. But they found themselves behind early in the second-half when Paqueta, who'd only been on the field for less than a minute, intercepted a poor clearance at the back and coolly slotted home the opener.
Brazil were in front but just two minutes later Gabriel Jesus was sent off for a nasty challenge on Eugenio Mena, giving Chile a numerical advantage which they used to pile on the pressure on the holders.
However, they couldn't find the back of the net, and Paqueta's goal got the job done. Brazil face Peru in the semi-finals on Monday. Here are the hits and flops from the match:
Hit: Neymar (Brazil)
The match-winner may have been Lucas Paqueta but Brazil's real inspiration behind the victory was Neymar. The PSG ace was in top form again and helped create the goal for Paqueta with some fine work on the ball, strengthening his case for the Copa America 'player of the tournament' prize.
With two goals and assists each in three games, Neymar came back into the starting XI after sitting out the Ecuador draw. He conjured up the highest number of chances with three, while Chile had no answer to his precocious dribbling skills besides just hacking the player down.
Flop: Charles Aranguiz (Chile)
It might have been easier to pick out Chile's attacking duo, Alexis Sanchez and Eduardo Vargas, for their inability to find the net. While both were dangerous and asked questions of Brazil's defense, Charles Aranguiz was a real disappointment.
He attempted just two crosses in the match, both of which failed to beat Marquinhos, and lost possession 10 times. While his passing range was impressive, nothing meaningful came of it.
Make no mistake, Aranguiz is a quality player, and has been a beacon of consistency for his side, even in this edition of Copa America so far, but Brazil's tight defense did a good job of negating his influence.
Hit: Lucas Paqueta (Brazil)
While he wasn't the best player in the match per se, Lucas Paqueta deserves credit for making an instant impact off the bench by clinically taking his chance which proved enough to sneak Brazil into the next round.
Coming on at half-time for the ineffective Roberto Firmino, the Lyon star cut the Reds open following a neat one-two with Neymar and intercepted a poor clearance from Mena to race in behind and slot home beyond Claudio Bravo for an unlikely match-winner.
Flop: Roberto Firmino (Brazil)
It's no secret that Roberto Firmino has had a tough Copa America campaign so far. Aside from his goal against Colombia, the Liverpool ace had little to show for his efforts and endured another poor outing against Chile before getting hooked off at half-time.
Starting behind Neymar in a more creative role, Firmino often ran out wide to stretch the Chilean defense open, and while he managed to do so to some extent, wasted a good chance in the first-half.
Following some good work in the build-up by Neymar, he lofted a fabulous cross into the far post for Firmino, but the Brazil number 20 sent it wide, robbing his PSG counterpart of what could've been a beautiful assist.
Hit: Arturo Vidal (Chile)
If this was indeed the last Copa America game of his career, Arturo Vidal may have signed off on a high. There were no trophies to celebrate but the player was a thorn in Brazil's defense, taking the game to the holders with his devastating link-up play whilst also working hard off-the-ball too.
He created two chances in the match and registered a pass completion rate of 86%. Vidal stationed himself high up the pitch, which kept the Brazilian defense on his toes.Once they were down to 10-men, Chile made life difficult for them, with much of the good work stemming from the Inter Milan man himself.
The only downside of his game, though, was how he cheaply conceded free-kicks and looked reckless at times. He even went into the book for hacking down Neymar with a cynical foul but can consider himself lucky not to have been sent off for the sheer number of fouls he gave away.