Steven Gerrard grabbed his 100th Liverpool goal to leave his side with their Champions League destiny in their own hands after a convincing 3-1 victory at Anfield.
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Robbie Keane scores against PSV and celebrates his first goal for Liverpool
Back-to-back games with Atletico Madrid now follow, and after the Spanish side's win over Marseille, those matches will almost certainly decide who wins the group.
Liverpool have won their first two group matches for the first time, and cruised to victory.
Robbie Keane scored his first goal for the club after 11 blank games since his £20million move from Tottenham, and Gerrard smashed home the third to grab his century of Liverpool goals.
And Dirk Kuyt got in on the act with his 10th goal in 16 Champions League games for the club.
But frankly, Liverpool never got out of second gear against the outclassed Dutch champions.
Benitez recalled Fabio Aurelio to left-back in place of Andrea Dossena, the only change from the side that won the Merseyside derby at Everton on Saturday.
It mean Javier Mascherano was left on the bench - despite recovering from a calf injury - for the manager's 250th game in control at Anfield.
PSV made three changes from side that beat Eredivisie bottom club Volendam at the weekend, with striker Danny Koevermans sacrificed for extra defensive strength.
Nordin Amrabat, Jason Culina and Otman Bakkal came into a side that included former Liverpool defender Jan Kromkamp.
With their side previously unbeaten this term, it was no surprise that there was an air of expectation around Anfield, and after four minutes the Kop got the start they wanted.
Gerrard's first corner, from the right, was met by a Fernando Torres first-time shot. He was criminally unmarked with Jeremie Brechet hopelessly adrift of his prey.
Somehow Andreas Isaksson blocked the Spaniard's effort, only for Dirk Kuyt to ram home the rebound from 10 yards.
Xabi Alonso tried another of his trademark 60-yard efforts, with Isaksson having to back-track to catch the ball, before Keane had a good penalty shout turned down when he was caught by Carlos Salcido.
Kuyt tested Isaksson again, this time with a 20-yard effort on the turn that the former Manchester City goalkeeper held low to his left.
Torres then headed wide from an Aurelio corner, before setting up Keane for his first Liverpool goal.
It came after 34 minutes when Kuyt's hard work sent Torres away down the right. When the low cross arrived in the box, it was met by Keane first-time, his shot speeding into the far bottom corner of the net.
Anfield erupted, Keane having finally netted on his 11th appearance for the club. His joy was obvious as he was mobbed by his colleagues.
PSV needed to do better after the break to rescue some pride. They brought on young defender Erik Peters for Jeremie Brechet, and at last started to come forward with some conviction.
Bakkal saw a 25-yard shot fizz just wide, before Salcido's tackle on Torres sent the Spaniard spinning to the turf, and a hush fell over the stadium until he struggled painfully to his feet.Amrabat, who had battled away bravely on his own in attack, then unleashed a fierce 20-yard effort which thudded just wide.
Torres should have ended the debate after 65 minutes when Kromkamp's wayward pass put him clear - but his flick past Isaksson drifted inches wide of the far post. The game was seemingly meandering to an inevitable conclusion, with Yossi Benayoun now on for Riera.
Gerrard was the next to try his luck, lifting a shot over from just outside the box, before Lucas replaced Keane. Dirk Marcellis was booked for a foul on Torres, and that paved the way for Gerrard to grab his 100th goal for Liverpool after 75 minutes, smashing a fierce 25-yarder past Isaksson, to the acclaim of the Kop.
But PSV hit back three minutes later, when substitute Balazs Dzsudzsak crossed from the right.The ball cleared Jamie Carragher to allow Koevermans to get to it ahead of Skrtel, and he headed past Jose Reina from 10 yards.
Ryan Babel replaced Gerrard with nine minutes to go - and the Reds comfortably saw out the closing stages of the match.
Back-to-back games with Atletico Madrid now follow, and after the Spanish side's win over Marseille, those matches will almost certainly decide who wins the group.
Liverpool have won their first two group matches for the first time, and cruised to victory.
Robbie Keane scored his first goal for the club after 11 blank games since his £20million move from Tottenham, and Gerrard smashed home the third to grab his century of Liverpool goals.
And Dirk Kuyt got in on the act with his 10th goal in 16 Champions League games for the club.
But frankly, Liverpool never got out of second gear against the outclassed Dutch champions.
Benitez recalled Fabio Aurelio to left-back in place of Andrea Dossena, the only change from the side that won the Merseyside derby at Everton on Saturday.
It mean Javier Mascherano was left on the bench - despite recovering from a calf injury - for the manager's 250th game in control at Anfield.
PSV made three changes from side that beat Eredivisie bottom club Volendam at the weekend, with striker Danny Koevermans sacrificed for extra defensive strength.
Nordin Amrabat, Jason Culina and Otman Bakkal came into a side that included former Liverpool defender Jan Kromkamp.
With their side previously unbeaten this term, it was no surprise that there was an air of expectation around Anfield, and after four minutes the Kop got the start they wanted.
Gerrard's first corner, from the right, was met by a Fernando Torres first-time shot. He was criminally unmarked with Jeremie Brechet hopelessly adrift of his prey.
Somehow Andreas Isaksson blocked the Spaniard's effort, only for Dirk Kuyt to ram home the rebound from 10 yards.
Xabi Alonso tried another of his trademark 60-yard efforts, with Isaksson having to back-track to catch the ball, before Keane had a good penalty shout turned down when he was caught by Carlos Salcido.
Kuyt tested Isaksson again, this time with a 20-yard effort on the turn that the former Manchester City goalkeeper held low to his left.
Torres then headed wide from an Aurelio corner, before setting up Keane for his first Liverpool goal.
It came after 34 minutes when Kuyt's hard work sent Torres away down the right. When the low cross arrived in the box, it was met by Keane first-time, his shot speeding into the far bottom corner of the net.
Anfield erupted, Keane having finally netted on his 11th appearance for the club. His joy was obvious as he was mobbed by his colleagues.
PSV needed to do better after the break to rescue some pride. They brought on young defender Erik Peters for Jeremie Brechet, and at last started to come forward with some conviction.
Bakkal saw a 25-yard shot fizz just wide, before Salcido's tackle on Torres sent the Spaniard spinning to the turf, and a hush fell over the stadium until he struggled painfully to his feet.Amrabat, who had battled away bravely on his own in attack, then unleashed a fierce 20-yard effort which thudded just wide.
Torres should have ended the debate after 65 minutes when Kromkamp's wayward pass put him clear - but his flick past Isaksson drifted inches wide of the far post. The game was seemingly meandering to an inevitable conclusion, with Yossi Benayoun now on for Riera.
Gerrard was the next to try his luck, lifting a shot over from just outside the box, before Lucas replaced Keane. Dirk Marcellis was booked for a foul on Torres, and that paved the way for Gerrard to grab his 100th goal for Liverpool after 75 minutes, smashing a fierce 25-yarder past Isaksson, to the acclaim of the Kop.
But PSV hit back three minutes later, when substitute Balazs Dzsudzsak crossed from the right.The ball cleared Jamie Carragher to allow Koevermans to get to it ahead of Skrtel, and he headed past Jose Reina from 10 yards.
Ryan Babel replaced Gerrard with nine minutes to go - and the Reds comfortably saw out the closing stages of the match.