Estevao scored a 95th-minute winner to earn Chelsea a 2-1 victory and inflict a third consecutive defeat in all competitions on Liverpool.
Liverpool were looking to bounce back from losses to Crystal Palace and Galatasaray having been knocked off top spot in the Premier League by Arsenal following their win over West Ham on Saturday.
However, the Reds were deservedly beaten when the Brazilian teenager Estevao turned home in added time, sparking wild scenes at Stamford Bridge, including from head coach Enzo Maresca, who was sent off for running down the touchline to celebrate with his players.
Arne Slot's side had to come from behind after Moises Caicedo blasted Chelsea ahead in the 14th minute with an unstoppable shot from the edge of the box that crashed into the top left corner.
Cody Gakpo delivered the equaliser in the 63rd minute when Alexander Isak's touch from Dominik Szobozlai's cross fell into the path of the forward to stab in.
Chelsea had the better of the first half, although struggled initially at the start of the second as their problems at centre-back continued with both Benoit Badiashile and Josh Acheampong forced off injured.
Florian Wirtz came on at half-time and lifted Liverpool, albeit only momentarily, with Mo Salah wasting two good opportunities before Chelsea finished much stronger.
They pushed for a winner late on with substitutes Jamie Gittens and Estevao both forcing Giorgi Mamardashvili, standing in for the injured Alisson, into saves before he tipped over from another long-range Caicedo shot.
Enzo Fernandez should have put Chelsea ahead, heading Estevao's cross against the outside of the left post, but the teenager tapped in from Marc Cucurella's low cross for their first win in four league games.
Redknapp: Liverpool missing Trent
Sky Sports' Jamie Redknapp:
"They've got problems at full-back. They're missing Trent (Alexander-Arnold).
"They haven't played the same right-back since the Burnley game. (Conor) Bradley had a tough 45 minutes. (Milos) Kerkez hasn't quite adapted either - the pressure of playing for Bournemouth isn't the same.
"They have problems all over the pitch but especially at full-back with (Andy) Robertson's injury at the end. This international break could be a good chance to reset."
Slot: I felt we would go onto win
Liverpool boss Arne Slot told Sky Sports:
"Their first chance - the only chance they had in the first half, if you can look at it as a chance, is a shot from 20 yards and goes into the top corner.
"I felt the game was even, maybe they were better in possession but we started off really well in the second half. It wasn't a surprise to me that we scored. I think in that period of time, I felt as if we could go one up in the last 10 to 15 minutes.
"It was an end to end game. We had chances to win it, they had chances to win it. And in the end again, we concede in the last second again."
Caballero: Maresca is happy - the players were fantastic
Chelsea assistant manager Willy Caballero on Enzo Maresca after his sending off: "He's OK. He's so happy now. Of course he cannot be here now but we are so happy that we achieved the three points in the last seconds. We are so happy and so proud. The players did a fantastic job. Now is a good break for many of them and hopefully we can recover a few more players and start the new cycle of games with energy."
On Maresca's celebration: "It's something special for any manager, no manager can hold inside what they feel. Unfortunately for him he was already on a yellow. We are all human beings. We have been players, we love to see that. For sure all of us we can learn from that as well."
On injuries to Badiashile and Acheampong: "They are OK. They were a little bit concerned about their situations but we talked with them and they are OK. They need this break to recover well."
Cucurella: We won the game with crosses
Chelsea defender Marc Cucurella told Sky Sports:
"We always try to attack no matter the situation. The way they play, Salah is always ready to attack, so we knew that crosses could be an advantage. We won the game in this way today.
"Estevao deserves this moment. It's never easy to adapt and he did so well."
