Victory with Atlético Madrid's goalless draw away to Marseilles ensured that Liverpool will enter the draw for the first knockout round in Nyon, Switzerland, a week on Friday as group winners.
It may still mean a meeting with Inter Milan, who finished second in group B behind Panathinaikos, or the likes of Juventus or Real Madrid, both of whom play this evening, but Barcelona and Roma, as fellow winners of their respective groups, are out of the equation and Liverpool will doubtless take comfort from the fact that the second leg will be at Anfield, which has proved such a potent weapon in this competition in recent years.
With qualification already assured before last night's game, Benítez made seven changes to the team who defeated Blackburn Rovers 3-1 in the Barclays Premier League last Saturday, but while his delight at solid performances from so many fringe players will surely be tempered by the knowledge that PSV are no one's idea of a Champions League team, there were plenty of grounds for optimism.
"We were talking about how important it was to have the second leg of the knockout round at Anfield and I'm pleased we've managed to do that," Benítez said. "There were a lot of positive things to come from the game, such as how the young players did. After they scored, we showed character to come back into the game."
Liverpool are undoubtedly stronger now than they have been at any point since Benítez's arrival 4½ years ago, but the dismal 4-2 defeat by Tottenham Hotspur in the Carling Cup fourth round last month, when several players on the periphery of the first team disappointed, left many wondering if they were strong enough.
If those questions were still being asked as the first half entered stoppage time, they will have eased when Ryan Babel equalised with a fine header and abated further as Liverpool took control after the interval, seizing the lead through a wonderful strike from Albert Riera, before David Ngog added a little gloss to proceedings with his first goal for the club.
It was beautifully created by Robbie Keane, who, restored to the starting line-up after being kept on the substitutes' bench against Blackburn, grew in confidence and influence as the game wore on and may feel as though he has turned a corner after an indifferent start to his Liverpool career.
It was so comfortable towards the end that the manager could even afford to blood three local lads, handing debuts to Martin Kelly and Jay Spearing and a third senior appearance to Stephen Darby.
Liverpool supporters had woken to the news that Babel had asked to join Ajax, his previous club, on loan in pursuit of more first-team football, but the Dutchman seemed determined to make a point against PSV. Dire against Blackburn three days earlier, Babel occasionally infuriated as only he can again last night, but his goal was just reward for his endeavour.
PSV had taken the lead on 36 minutes. Dirk Marcellis did not know what day it was when Balazs Dzsudzsak's corner hit him on the chest, but it had the desired effect of diverting the ball into the path of Danko Lazovic, who poked the ball under the legs of Diego Cavalieri in the Liverpool goal.
Falling behind seemed to prompt Liverpool into life and they never surrendered the momentum thereafter. Lucas Leiva was calm and composed in central midfield and it was from the Brazilian's free kick that Babel rose above Otman Bakkal to score with a perfectly timed and directed header. It was the 300th goal scored by Liverpool in European Cup competition.
There was better to follow, when Riera collected the ball 30 yards out and drilled a shot into the top corner, before Ngog was sent racing clear by Keane's deft through-ball and finished calmly.
"I think Ngog has a big future here," Benítez said. "Of course, the strikers always want to score, but Robbie worked very hard for us up front." Liverpool march on.