In a match which had already seen two red cards, Alisson was given his marching orders by the referee after a high boot connected with Ecuador's Enner Valencia in the 26th minute.
However, VAR decided that getting the ball first was enough to save the Reds goalkeeper, despite where his foot ended up, and the punishment was downgraded to yellow.
Then, right at the death, after Felix Torres had cancelled out Casemiro's opener, Alisson was shown red once again.
A punch in the box caught Ayrton Preciado in the forehead and Ecuador thought they had the chance to win an ill-tempered match from the spot in injury time.
However, Alisson was spared for the second time, with VAR ruling he got the ball.
"I think this was the first time this has happened in the history of football," a grateful Alisson said after the game.
"I think that I acted properly in the moves and I think my team mates helped me a lot, they were incisive in their complaints to the referee. This shows once again the importance of using VAR in football.
"I am happy with the VAR, if it wasn't for the VAR we'd have been punished unfairly."