Liverpool will be seeking its sixth European title when it faces fellow English club Tottenham on Saturday in Madrid.
Messi earned the honour, which goes to the leading scorer in league matches in Europe’s top divisions, for a record-extending sixth time after finding the net 36 times for Barcelona, while Mbappe ended the campaign on 33 goals.
Barcelona extended its unbeaten streak at home in Europe's elite club competition to 32 straight matches, a run that started in 2013.
Barcelona continued their preparation, on the eve of their Champions League semi-finals first leg clash with Liverpool at Camp Nou.
Thanks to Messi, Barca have swelled their league trophy count to 26, closing to within seven of Real Madrid's record 33. Before Messi came of age, Real Madrid had 31 titles while Barca had 18.
After an excellent start, United were undone twice in four minutes by Messi, who first nicked the ball off the careless Ashley Young and then watched as a weak shot from distance squirmed underneath David de Gea.
Messi shows flashes of brilliance but it was not his night as Venezuela put three past their more illustrious rivals for the first time with goals from Salomon Rondon, Jhon Murillo and Josef Martinez.
Messi opened the scoring with an unstoppable free kick then combined with devastating effect with Luis Suarez to carve Betis open and score a second goal right before halftime.
Barca won a penalty early in the second half when Luis Suarez was fouled and Messi converted to put the league leaders in front and the Uruguayan forward made sure of the points with a simple finish from close range in the 82nd minute.
Luis Suarez scored twice as Barcelona inflicted another defeat on Real Madrid to move within touching distance of winning a record fifth consecutive Copa del Rey.
Lionel Messi scores his 50th hat trick for club and country, in a 4-2 victory at Sevilla, helping Barcelona to take a big step toward retaining the Spanish league title.
Santiago Solari marks his 100th day in charge of Real Madrid with a 1-1 draw at Barcelona in the Copa del Rey, 101 days after his predecessor's reign ended with a 5-1 thrashing to the Catalans.
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