Messi had equalled German legend Gerd Mueller's mark of 85 goals from 1972 when he slotted the ball home in the 16th minute of La Liga clash at Real Betis from a pass by Adriano.
The 25-year-old then added a second in the 25th minute from an Andres Iniesta backheel nine minutes later to claim the record.
Messi has made a habit of shattering records in his career.
Last season, he became the most successful goal scorer in the history of the La Liga by hitting 50 goals in the league campaign.
He is already the club's greatest scorer having gone past the record held by Cesar Rodriguez set in the 1940s and 1950s.
Messi last season equalled the record for goals scored in a Champions League season when he hit 14.
His latest feat means he will be the overwhelming favourite to once again claim the Ballon d'Or where he faces competition from Iniesta and Real Madrid's Cristiano Ronaldo.
Messi would be the first player to win the award four times.
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