Star man Messi became the most prolific goalscorer for a single club in the competition as he scored one and assisted the other in a 2-1 victory that confirmed Barca as Group B winners.
Messi is now leading the way with six goals this season in the Champions League, amazingly averaging a goal every 45 minutes.
The Spanish champions did double their lead in the 70th minute, however, when Pique steered a clever Messi free kick into the bottom corner of the net.
Despite winning the game, Barca spent large parts of the match on the back foot.
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PSV had two golden chances of their own late in the first half, but Luuk de Jong saw his towering header hit the crossbar before Denzel Dumfries somehow failed to bundle the rebound home. We gifted them too many counter-attacks and free kicks and they had a lot of chances. This goal is not even a surprise to see anymore from the Argentine but we should not play down just how hard and spectacular this goal is.
Both Barcelona and Juventus have booked their spot in the Champions League knockout round ahead of Match Day 6. PSV is 0-1-3, and while it would have liked to make the round of 16, the goal probably has shifted to trying to finish in third and enter the Europa League.
Ronaldo collected his fifth award previous year, but appears unlikely to retain his crown and move ahead of bitter rival Messi.
Valverde started Clement Lenglet in defense instead of Samuel Umtiti, who returned to play at the weekend for the first time since the end of September due to a left knee injury, but felt discomfort in the knee in training Tuesday.
Barcelona has won its Champions League group a record 20 times, and only a dramatic reversal of form will keep the Blaugrana from adding to its prestigious mark.