Quickfire goals from Mohamed Salah and Naby Keita had the Reds 2-0 up by 13 minutes. A double from Antoine Griezmann restored parity before half-time. But the Frenchman was sent off early in the second half for smashing his studs into Roberto Firmino's face, handing the visitors a numerical advantage.
Miguel Hermoso then conceded a penalty after bringing down Diogo Jota inside the box, and Salah made no mistake from 12 yards to restore Liverpool's lead on the night.
Los Rojiblancos also appeared to have got a penalty themselves just four minutes later when Jose Gimenez went down under pressure from Roberto Firmino. However, following a VAR review, that call was overturned.
Liverpool eventually held on to the win to come away with all three points, beating Atletico Madrid in the competition for the very first time. On that note, here are the five major talking points from the game:
#5 High-profile game lives up to its billing
There were many games kicking off at the same time on the night. But Atletico Madrid's game against Liverpool was still touted as the match to keep an eye on. Suffice to say, the game didn't disappoint.
Goals galore (some of which were spectacular), a thrilling comeback, a red card and some controversial VAR decisions - this game had all the makings of a Champions League classic.
Liverpool and Atletico produced a thriller last year at Anfield. Now they have given us a thriller in Madrid, making the fixture live up to its billing.
#4 Mohamed Salah sizzles for Liverpool again
Mohamed Salah has been in a rich vein of form coming into the match, and he continued that with a brace against Atletico.
Make no mistake, this wasn't the most vintage performance from the star. In fact, Salah was not at his sublime best. However, he had only two real chances in the game, and buried both. That's what sets him apart from the rest.
His first goal had a bit of fortune, as it took a slight deflection on its way in. But the power with which he struck that shot was incredible. Same with his penalty, as the Egyptian ace thumped a low drive into the bottom corner.
On both occasions, Salah's strikes put Liverpool in front, his penalty eventually proving to be the winner. That provided another example of how valuable Salah is to his side. His goalscoring streak now extends to nine games across competitions, the first by a Liverpool player in the club's illustrious history.
#3 VAR madness adds to the thrill at the Wanda Metropolitano
The game between Liverpool and Atletico Madrid was fast and thrilling enough. Nut two huge VAR decisions only took it up a few more notches, and both came in the closing period of the game.
In the 56th minute, Antoine Griezmann, Atletico's hero of the night until then with a confident brace, was sent off for a studs-up challenge on Roberto Firmino. The referee didn't hesitate to pull out a red card immediately, but the incident was still consulted with the assistant referees.
Replays showed there was a clear foul, but the contact didn't seem hard enough.
A yellow card might have sufficed. And if that wasn't enough, much to Atletico's disappointment, they also had a penalty overruled late on.
Jose Gimenez appeared to go down under pressure from Diogo Jota after a free-kick was played by Renan Lodi, leading to a penalty. However, the match official consulted the pitchside monitor, and deemed that the Uruguayan went down too easily, which was another controversial call.
#2 Antoine Griezmann is tailor-made for Atletico Madrid
Sure, he has been poor since returning from Barcelona in the summer. But with a brace against Liverpool, the Frenchman rolled back the years to the good old days of his first stint at the club.
Also, not to mention, both of Griezmann's goals came after Liverpool were leading 2-0. That helped Atletico Madrid come back into the match before half-time.
While his first strike was scrappy, the Frenchman exposed Liverpool at the back for his second. Griezmann cleverly evading the Liverpool defence after latching onto a through-ball from Felix, and dispatching a diagonal shot beyond Alisson. Could that spark a return to form for the beleaguered star?
#1 Liverpool remain in control of Group B
With three wins from three, Liverpool are running away with the group. No one else is remotely close to them. Atletico, who were also unbeaten before this game, are now five points behind the Reds.
It wasn't a perfect game for either side, but Liverpool took their chances in the match and weathered a late storm to take all three points. They can be excused for thinking they have one leg in the knockout stages. But the Reds still have one more game left against both Atletico (home) and Milan (away).
Grinding out results even when not at their best is the hallmark of a true champion team, and Liverpool showed that quality once again on the night. Would that be enough for them to go all the way this season remains to be seen, though?