Rafa Benitez made a host of changes, resting Reina, Gerrard, Alonso and Kuyt and giving Cavalieri, Lucas, Babel, Ngog and Keane opportunity to shine.
The Reds went behind despite controlling most the first half against a poor PSV side, but Ryan Babel’s glancing header from a Lucas free-kick on the stroke of half time sent the sides in level at the break.
The second half was much improved and Albert Riera scored his first European goal for the club with a stunning strike from 25 yards into the top corner. And the lively Robbie Keane soon set-up youngster David Ngog for the Frenchman to slot home and make it 3-1.
Keane again played a great ball for Lucas moments later but the Brazilian couldn’t finish. He, along with Dossena at the back, enjoyed good performances.
Further success arrived in the form of three academy players coming on as subs; Stephen Darby at right back, Jay Spearing in midfield and Martin Kelly at centre back. All three did well and looked comfortable.
The added bonus to the night was winning the group, which means the second leg of the knockout stage will be played at Anfield.
BBC Sport Report
PSV took the lead when Danko Lazovic poked in from close range after Javier Mascherano failed to clear a corner.
Ryan Babel equalised with a glancing header from Lucas Leiva‘s cross and Albert Riera put them ahead with a 25-yard drive that found the top corner.
PSV’s Dirk Marcellis hit a post, before David Ngog latched on to Robbie Keane’s pass and slotted in to seal the win.
Liverpool‘s victory was reward for a much-improved performance after the interval.
It also gave manager Rafael Benitez his wish to claim top spot in the group, which means Liverpool will play the second leg of their last 16 match at Anfield.
Benitez had made clear before the match that it was important to achieve that, but he still sent out a team with seven changes from Saturday’s win against Blackburn.
And unsurprisingly, there was little fluency about Liverpool‘s play early on, with only Riera looking bright and alert.
There was little to admire in PSV’s work, either, as the Dutch side could do no more than match Liverpool‘s lethargic tempo.
Timmy Simons’ drive was comfortably beaten away by Diego Cavalieri as the hosts finally got a shot in on goal.
With an absence of creativity and urgency it was hard to see where a goal might come from.
Yet PSV got themselves in front when Mascherano missed his header as he tried to clear a corner and the ball fell for Lazovic, who stroked the ball past Cavalieri.
Liverpool finally found some rhythm and David Ngog had a chance to equalise but headed straight at Andreas Isaksson.
There was no such profligacy from Babel in first-half injury time when his downward header bounced into the top corner to put Liverpool on level terms.
After the break, Liverpool pressed for another goal and they might have had one Babel had released Keane rather than opted to shoot.
But when the goal came, it arrived in emphatic style when the impressive Riera struck a magnificent shot from distance that flew into the top corner.
PSV responded and Marcellis struck the outside of the post from a tight angle.
But any hopes the Dutch side had of a comeback were dashed when Keane played an inch-perfect pass through to Ngog and he produced a composed low finish to score his first goal for Liverpool.
Liverpool might have won by an even greater margin but Lucas missed a good chance after Keane had again fashioned the opportunity.
PSV: Isaksson, Culina, Marcellis, Brechet, Salcido, Mendez (Manco 80), Simons, Dzsudzsak, Bakkal (Nijland 83), Lazovic, Amrabat (Koevermans 72).
Subs Not Used: Cassio, Rodriguez, Pieters, Wuytens.
Booked: Simons, Mendez.
Goals: Lazovic 36.
Liverpool: Cavalieri, Arbeloa (Darby 69), Carragher (Kelly 81), Agger, Dossena, Mascherano, Leiva Lucas, Babel, Ngog, Riera (Spearing 76), Keane.
Subs Not Used: Reina, Gerrard, Alonso, Benayoun.
Booked: Riera, Arbeloa, Dossena.
Goals: Babel 45, Riera 69, Ngog 77.
Referee: Nikolai Ivanov (Russia)
Next Match: Hull City (h) Saturday, 3pm