Messi was left out of the Blaugrana starting line-up as they looked to end their run of four league fixtures without a win at Camp Nou.
He was however introduced at half time with the scores at 1-1.
Messi made an immediate impact, teeing Antoine Griezmann up with a wonderful dummy before scoring twice himself.
Teenage sensation Pedri rounded off Barca’s 5-2 win in stoppage time.
“We talked to Leo, who came out of the Dynamo [Kyiv] game with a niggle and he was not fit to play from the start,” Koeman explained to reporters after the final whistle.
“He was on the bench in case we needed him. If he was physically OK, he would have played from the start.”
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