The hosts started well and took the lead with a controversial goal from Danko Lazovic, but Liverpool pulled level through Babel seconds before the break and took over in the second period. Atletico Madrid's goalless draw at Marseilles ensured that Rafael Benitez's side would top their group.
Liverpool left Steven Gerrard, Xabi Alonso and Jose Reina on the bench as Benitez recalled Robbie Keane to play up front alongside Ngog, with Babel included on the wing and Lucas starting in midfield. Diego Cavalieri got a rare start in goal, with Jamie Carragher captaining the side.
Benitez was able to enjoy the second half, giving European debuts to three locally produced youngsters, Stephen Darby, Jay Spearing and Martin Kelly. Benitez said: "We wanted to win the group to make sure that we had the second leg of the next round at Anfield.
"And there were so many positive things to take from this performance. We were able to use three young lads, and the performances of two other young players, Lucas and Ngog, were outstanding. We were able to make a lot of changes and all the players coming in did well."
Yet PSV went ahead after 36 minutes, punishing some poor Liverpool defending from a corner. Javier Mascherano failed to clear at the near post, and Danko Lazovic pounced on the loose ball to crack the ball in through the legs of Cavalieri. Duly roused, Liverpool managed to draw
level when Lucas' free-kick from the right was met with a glancing header by Babel, the ball bouncing just in front of Andreas Isaksson in the PSV goal. The keeper got his hand to the ball but could only push it into the net.
Babel, so often a peripheral figure when he features in Liverpool's starting line-up, was showing far more intensity, forging another chance for himself after 59 minutes when he cut in and fired a low shot into the side-netting. PSV still needed the win, though, and kept coming forward at pace. It took a fine saving header from Alvaro Arbeloa to stop Nordin Amrabat reaching a far-post cross.
After 67 minutes Edison Mendez was cautioned for following through into Lucas' ankle, and two minutes later Liverpool were ahead when Riera hammered a 30-yard shot past Isaksson.
Within eight minutes the result was put beyong reasonable doubt when Keane's fine ball sent Ngog racing away from the halfway line to coolly slide in the third.