Messi, 31, netted the opening goal which proved to be the 106th of his Barcelona career, overtaking Ronaldo's tally of 105 for Real Madrid.
Messi has now scored six Champions League goals this season, moving him past Eden Dzeko and the Roma star's five finishes to lead the goalscoring chart through five rounds of group stage play.
He then turned supplier for Barcelona's second, taking a free kick that Gerard Pique deflected past Zoet. Barca has some room for error entering this contest but will look to end a wineless streak, while PSV knows it must win this game to have any chance of getting through to the knockout stage or finishing third and entering the Europa League. The draw allowed Sevilla to pass Barcelona for first in La Liga. They will undoubtedly field a very good team and want to win this game as well.
Marc Andre Ter Stegen's long wait for a clean sheet extended for a further 90 minutes at least after he failed to stop de Jong's goal for the home side. We gifted them too many counter-attacks and free kicks and they had a lot of chances. The team has just one point from five matches and is guaranteed to finish bottom of the group.More news: India bus crash: Mandya, Karnataka smash 'leaves 25 passengers dead'
Ronaldo collected his fifth award past year, but appears unlikely to retain his crown and move ahead of bitter rival Messi.
The Champions League match between PSV Eindhoven and Barcelona will be broadcast live on B/R Live.
Missing the injured Luis Suarez, Messi was operating in the number nine role for Barcelona, and the Argentine started to see more of the ball as the first half developed.
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.