"PSV are strong, experienced and with an experienced manager," he said as reported by Sky Sports on Tuesday.
"They beat us last season and we need to rectify that memory."
Though Liverpool is slotted as a favorite to progress, the Spaniard willingly outlined PSV Eindhoven players he felt were a particular threat during the match-up.
"Our former player Jan Kromkamp will be playing, and also I remember Benfica when Ronald Koeman was there then," he said.
Liverpool has struggled recently after their shameful 3-0 derby defeat to Everton, and Benitez admitted improvement was needed in order to face the side's challenging group opponents.
"The group is dangerous, Bordeaux and Galatasaray are both good sides. If we play like we did last season then qualification is achievable but we need to solve our problems," Benitez admitted.
With having already stacked Liverpool's striking talent with fresh summer purchases Craig Bellamy and Dirk Kuyt, Benitez is ready to turn his attention to the defense.
"For me we must improve in defense. That means that when you are strong there you have more possession, chances and the opportunity to play on the counter-attack," he said.
"We must become a very solid and consistent team and then, with the quality we have up front, I know we will score plenty of goals."
Benitez might have an uphill battle after the last derby match.
England defender Jamie Carragher and Jose Reina were the players predominately faulted for the sizeable loss, but Benitez refused to blame them, instead claiming international games and exhaustion as the main culprits.
"It is more difficult to find the right team and balance with players returning from injury and from internationals," said Benitez.
"The problem was not that we used Carra, but that we used so many players coming back from international games as well. Altogether, that was a gamble.
"They all had very hard periods away with their countries, playing two games. They are all big names and we decided to mix things up with players who had not been away and those that had," he added.