The 20-year-old Brazilian fired the 13-times European champions into the lead in the 27th minute at the Alfredo di Stefano stadium after controlling a long diagonal pass from Toni Kroos from his own half which flummoxed the Liverpool defence.
Marco Asensio put the hosts further at ease by scoring in the 35th after a Kroos pass again caused havoc among the visiting backline but Liverpool looked more settled after the interval and a scrappy Mohamed Salah strike pulled them back into contention early in the second half.
But they failed to build on their momentum and Vinicius, who has a reputation for thrilling play but a lack of composure in front of goal, struck again in the 63rd minute, blasting past Liverpool keeper Alisson after clever combination play between Karim Benzema and Luka Modric.
Asensio missed a clear chance to grab Real’s fourth goal, while Liverpool threatened late on.
Yet the visitors were unable to find a second away goal to take back with them to Anfield next Wednesday and the game ended with the same scoreline as in the 2018 Champions League final.
Vinicius, who kissed the Real badge after scoring his first goal was pleased to finally deliver on the biggest stage of all and silence the doubters who claimed he lacked the bottle to succeed at Real.
“The people on the outside can keep talking but I kept on working, that gave me the strength to rise to an important occasion and get the goals we needed,” he told reporters.
Real coach Zinedine Zidane added: “That felt great, we played superbly but then had problems in the second half but recovered and produced a great performance, I’m so proud of the players. But there’s still the second leg to come.”
Real were dealt a huge setback on the morning of the game with the news that Raphael Varane had tested positive for Covid-19, leaving Zidane’s side without their two top centrebacks as captain Sergio Ramos watched on injured.
But it was the heart of Liverpool’s defence, depleted for the majority of the season and composed in Real of the inexperienced Nathaniel Phillips and Ozan Kabak, that suffered the most pain.
Kroos’s incisive ball from deep caught out Phillips as Vinicius controlled it with his shoulder before confidently slotting past Alisson.
Liverpool were soon caught out again by a Kroos pass, a panicked Trent Alexander-Arnold heading the ball to the feet of Asensio, who chipped Alisson then followed his shot into the net.
Not sharp enough
“Two moments of not concentrating enough and they scored. We weren’t sharp enough,” said midfielder Georginio Wijnaldum.
“We hoped for a better result.”
Visiting coach Jurgen Klopp brought on Spain midfielder Thiago Alcantara for Naby Keita before halftime and his side looked more settled after the interval, with Salah deservedly pulling them back into contention.
But they again made things too easy for Real, who live for Champions League knockout matches and looked as at ease here at their tiny empty training ground as they do on these occasions at a bursting Santiago Bernabeu, currently under reconstruction.
“If you want to go to the semifinal, you have to earn the right to do so. We didn’t do that tonight, especially in the first half,” said Klopp.
“The only good thing I can say, apart from the goal, is it’s only the first half of the tie.”
Liverpool will take solace from the fact they managed to overturn a 3-0 deficit against Barcelona in the semifinals in 2019 but in the second leg they will be unable to count on the scorching atmosphere at Anfield, where they have lost their last six league games.