Messi struck twice in the victory over Real Mallorca, to take him past the Brazilian great who scored 75 in 1958 for Santos and Brazil.
Messi is now nine behind German star Muller, who has the all time record with Bayern Munich and West Germany from 1972.
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The reputation of the Premier League means it is the most popular and one of the most watched leagues in the world.
Five English clubs will compete in the last sixteen of the Champions League for the first time ever as Liverpool, Manchester United, Manchester City, Chelsea and Tottenham face some difficult away matches.