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.
Then, Marco Asensio added the second in the 35th minutes after a Kroos pass again which was headed towards goal by Arnold and Asensio raced to chip Alison Becker.
Mohamed Salah strike pulled them back into contention early in the second half but Vinicius struck again in the 63rd minute to to put his side in pole position for next week's second leg at Anfield.
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