The 27-year-old reached the milestone when he scored on the stroke of half-time to cancel out Sergio Garcia's opener for Espanyol, before adding his second five minutes after the interval.
Gerard Pique notched Barca's third three minutes later to put them firmly in control, before Pedro added gloss to the scoreline, and Messi turned it into a rout as he followed up hat-tricks against Sevilla and Apoel Nicosia with another three-goal haul.
Messi, who recently became the leading scorer in Primera Division history, has now scored 402 goals in competitive and friendly matches for Barca.
Messi's treble came just 24 hours after Cristiano Ronaldo set a new Primera Division record of 23 hat-tricks, but Enrique was just as impressed with his star's overall contribution as he was with his goal scoring exploits.
"Today (Sunday), he's done that scoring goals but also he's created chances and he's also worked very hard defensively.
"He's shown maximum commitment as he has done since the start of the season."
Enrique pinpointed Messi's first goal as being crucial to swinging the match in Barcelona's favour as the Catalans won their seventh straight match in all competitions.
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