Liverpool can all but end PSV's Champions League interests with a victory that would put them on the brink of qualification for the next round.
The Dutch side arrive at Anfield on Tuesday for the second round of matches in Group D already smarting after being comprehensively beaten 3-0 in their opening home match with Atletico Madrid.
At the same time, Liverpool were winning 2-1 in Marseille, thanks to a Steven Gerrard double, to give themselves a flying start to the group matches.
And for PSV and their coach Huub Stevens, history is certainly not on their side.
Stevens admits his side have to learn fast from the disastrous defeat by Fernando Torres' former Madrid pals.
He said: "It was really disappointing to start the campaign with such a heavy home defeat.
"We know we just have to learn from what happened, because going to Liverpool will be even more difficult.
"But we have only played one match, there are still five to go so we can turn this round."
He added: "We can learn a lot. Madrid struck against us at the right moments, and we must not let Liverpool do the same to us."
However, PSV's record against Liverpool hardly gives a reason to be confident.
The two clubs had never met until the 2006-07 campaign, when they faced each other four times.
In the group stage, they played out a goalless draw in Eindhoven before Liverpool won the return match 2-0 through goals from Gerrard and Peter Crouch to secure first place in the section.
Rafael Benitez's team then earned a comprehensive 4-0 aggregate victory in the quarter-finals. Gerrard, John Arne Riise and Crouch all found the net in a 3-0 first-leg triumph in the Netherlands before Crouch struck the only goal of the return.
On a personal note, Stevens has never won a match in England, be it on the field or in the dugout.
As a player with PSV, he tasted defeat in UEFA Cup games at Wolves (1980/81), Nottingham Forest (1983/84) and Manchester United (1984/85).
As a coach, Stevens' Schalke side lost 3-2 at Arsenal in the 2001/02 Champions League group stage, with a subsequent 3-1 home win against the Gunners not enough to save them from elimination.
The next year he did enjoy some success with Hertha Berlin against Fulham in the UEFA Cup third round, holding out for a goalless draw in London following a 2-1 home victory.
If the tie goes to form and history, Liverpool will have six points by the end of the week, while Atletico Madrid must be confident of also beating Marseille at home.
That would leave the two group favourites six points ahead of PSV and Marseille with four games left each. If Liverpool then win their two final home games, qualification will be virtually assured.
Benitez maintains the crunch will come when Liverpool go to Madrid on October 22, saying: "If we can win our first two games and then not lose in Madrid, qualification will be within our grasp."
PSV keeper Andreas Isaksson may have his own personal fears over Tuesday's clash. The last time he faced Torres was when the Spaniard scored in a 2-1 win against Sweden in a Euro 2008 group match.
Isaksson's last match in England was Manchester City's 8-1 mauling at Middlesbrough on the final day of last season, with the keeper soon to be sold to PSV for £800,000.
The Dutch side arrive at Anfield on Tuesday for the second round of matches in Group D already smarting after being comprehensively beaten 3-0 in their opening home match with Atletico Madrid.
At the same time, Liverpool were winning 2-1 in Marseille, thanks to a Steven Gerrard double, to give themselves a flying start to the group matches.
And for PSV and their coach Huub Stevens, history is certainly not on their side.
Stevens admits his side have to learn fast from the disastrous defeat by Fernando Torres' former Madrid pals.
He said: "It was really disappointing to start the campaign with such a heavy home defeat.
"We know we just have to learn from what happened, because going to Liverpool will be even more difficult.
"But we have only played one match, there are still five to go so we can turn this round."
He added: "We can learn a lot. Madrid struck against us at the right moments, and we must not let Liverpool do the same to us."
However, PSV's record against Liverpool hardly gives a reason to be confident.
The two clubs had never met until the 2006-07 campaign, when they faced each other four times.
In the group stage, they played out a goalless draw in Eindhoven before Liverpool won the return match 2-0 through goals from Gerrard and Peter Crouch to secure first place in the section.
Rafael Benitez's team then earned a comprehensive 4-0 aggregate victory in the quarter-finals. Gerrard, John Arne Riise and Crouch all found the net in a 3-0 first-leg triumph in the Netherlands before Crouch struck the only goal of the return.
On a personal note, Stevens has never won a match in England, be it on the field or in the dugout.
As a player with PSV, he tasted defeat in UEFA Cup games at Wolves (1980/81), Nottingham Forest (1983/84) and Manchester United (1984/85).
As a coach, Stevens' Schalke side lost 3-2 at Arsenal in the 2001/02 Champions League group stage, with a subsequent 3-1 home win against the Gunners not enough to save them from elimination.
The next year he did enjoy some success with Hertha Berlin against Fulham in the UEFA Cup third round, holding out for a goalless draw in London following a 2-1 home victory.
If the tie goes to form and history, Liverpool will have six points by the end of the week, while Atletico Madrid must be confident of also beating Marseille at home.
That would leave the two group favourites six points ahead of PSV and Marseille with four games left each. If Liverpool then win their two final home games, qualification will be virtually assured.
Benitez maintains the crunch will come when Liverpool go to Madrid on October 22, saying: "If we can win our first two games and then not lose in Madrid, qualification will be within our grasp."
PSV keeper Andreas Isaksson may have his own personal fears over Tuesday's clash. The last time he faced Torres was when the Spaniard scored in a 2-1 win against Sweden in a Euro 2008 group match.
Isaksson's last match in England was Manchester City's 8-1 mauling at Middlesbrough on the final day of last season, with the keeper soon to be sold to PSV for £800,000.
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