The 22-year-old Kylian Mbappe's goals in the round of 16 first-leg tie made him the first-ever player to score a hat-trick against Barcelona in the knockout stages of the Champions League.
Messi had sat out the previous two games suspended after being sent off in the Spanish Super Cup final defeat by Athletic Bilbao but looked refreshed and ultimately made the difference again.
La Liga champions top the list among Europe's major leagues with $832 million (681.2 million euros), followed by Bayern Munich, Liverpool and Paris St Germain.
Meanwhile, Lionel Messi and Antoine Griezmann each scored twice as Barcelona thrashed Granada 4-0 away to win a third consecutive La Liga game for the first time this season.
Talking about his future Lionel Messi says he has no plans to become a coach when he retires from playing, and adds that he is more interested in being a director of football than working in the unforgiving world of football management.
Messi's Barcelona were top of the Spanish football league with 11 games to go when last season was disrupted by the Covid-19 pandemic, but the Catalans lost the title to Real Madrid when play later resumed in empty stadiums.
A third consecutive league win took third-placed Real on to 26 points after 13 games, level with second-placed Atletico Madrid and leaders Real Sociedad but having played two games more than Atletico.
Real Madrid’s struggles in the Spanish league continued as city rivals Atletico moved level with leaders Real Sociedad after extending their winning run to six matches.
The two members of Atletico Madrid's group were set to travel to Portugal for the Champions League quarterfinals against RB Leipzig in Lisbon.
Barca once again failed to build on an early advantage and were forced to grind out the victory in the second half as Valladolid took the game to them.
Substitute Ivan Rakitic scores in the 71st minute to help Barcelona win 1-0 against Athletic Bilbao bringing the Catalans back to the top of the La Liga. Second placed Real Madrid face Real Mallorca on Wednesday.
The second of Europe's five major leagues, La Liga, kicked off in Spain as two local rivals, Sevilla and Real Betis met in a hotly contested derby behind closed doors.
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