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PSG led early Thursday morning (AEDT) in the Group C shock when Juan Bernat capitalized on a mediocre defense and his hosts doubled their advantage with a record goal for Neymar.
Neymar scored his 31st goal in the Champions League, allowing him to stand out from Kaka as the most prolific Brazilian in the history of the competition.
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James Milner was awarded a penalty on his 150th appearance in Liverpool, but Jurgen Klopp's team failed to equalize at Parc des Princes and must now beat billiard leader Napoli to Anfield on the sixth day for a chance to progress.
Angel Di Maria forced Alisson to make a quick stop and the goalkeeper was back in the fight, Neymar firing on his Brazilian international compatriot.
Alisson was beaten in the 13th minute, however, Bernat went into the bottom left corner after grabbing the ball lost by Virgil van Dijk.
Mohamed Salah opened fire before Marco Verratti may have the chance to be held for a powerful tackle against Joe Gomez.
PSG raised the score to 2-0 while Neymar scored the rebound when Alisson managed to avoid Edinson Cavani's poor result after a quick attack, but Liverpool recovered a goal behind the ball.
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Sadio Mane was seduced by Di Maria's challenge, referee Szymon Marciniak giving a corner and then changing his mind, and Milner sent Gianluigi Buffon upside down.
Marquinhos had a third for PSG rightly excluded shortly after the restart and Roberto Firmino missed a good opportunity for visitors.
Klopp pitched Daniel Sturridge and Xherdan Shaqiri, offensive substitutes, looking for an equalizer, but PSG held on to take revenge for Anfield's 3-2 defeat in September.
What does it mean? Liverpool in trouble
The last season's finalists have not yet come out, but they have a tough job getting a spot in the knockout stages of the Champions League. The leaders of Group C, Napoli, go to Anfield and Liverpool must win this match to progress in place of Carlo Ancelotti's team.
Neymar dazzles on the big stage
The expensive crown jewel of PSG did not always produce its best performance when his team needed it, but Liverpool could not handle Neymar. The Brazilian has caused countless problems in the Reds' defense and could easily have done more than his lone goal of scoring the story, but Van Dijk may have the chance to not concede a late penalty .
Henderson loses the battle of Verratti
Liverpool protested that Verratti should have been fired for a serious foul on Gomez, but the Italian international dominated the midfield with a fine performance. Liverpool captain Jordan Henderson, sent to Watford this weekend, was unable to approach his direct opponent.
And after?
Next month, on the sixth day, Napoli will host Napoli, while PSG will attempt to qualify for Red Star. The Reds play Everton in the Merseyside derby at Anfield on Sunday, while PSG head to Bordeaux.
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