Old Trafford instead became a stage for Kylian Mbappe to shine in tandem with Angel Di Maria, who relished the revenge mission on his return to his former club.
Paris Saint-Germain will be without Neymar and Thomas Meunier against Manchester United while Edinson Cavani's participation also remains a major doubt on Tuesday at Old Trafford.
PSG will be without the world's most expensive player Neymar and possibly 192-goal, all-time club leading scorer Edinson Cavani against a revitalized United side unbeaten under their new coach Ole Gunnar Solskjaer.
Despite the setback, PSG leads second-placed Lille by 10 points, having played two games less.
Neymar was injured while playing against Strasbourg last Wednesday in the French Cup, rolling his ankle as he fell to the ground following a couple of challenges.
PSG will travel to Manchester for the first leg of the Champions League round of 16 clash on February 12.
PSG is set to take on host Manchester United on February 12 in the first leg of the last-16 of Champions League.
PSG had won the past five League Cups, however, it was bottom placed Guingamp that upset the defending champions and are 36 points behind the star-studded club.
Neymar was on the sidelines during PSG's 2-1 win over US Orleans in the Coupe de la Ligue round of 16.
Areola arrived at the club's academy in 2006 before rising through the ranks of PSG's youth system.
Cavani and Neymar were both assisted by their 19-year-old teammate, with Mbappe putting on an excellent display of speed, strength and dribbling throughout the game.
Liverpool lost their third match in the group as they went down 2-1 to PSG and now are staring at an early exit from the Champions League.
Neymar was substituted with an apparent groin injury during the first half of Brazil's friendly against Cameroon.
Paris Saint-Germain will play Liverpool on Wednesday in their Champions League fixture at the Parc des Princes.
PSG says the Italy international "made a spontaneous apology to the coach and the management of Paris Saint-Germain" and will be "deprived of a portion of his monthly ethics bonus."
The atmosphere in the southern city of Naples is likely to be hostile, in particular for Buffon as a former Juventus player.
The 19-year-old star of France's World Cup title run this year, Mbappe became the youngest player to score four goals in a French league match in 45 seasons.
Neymar was caught by Wylan Cyprien's flailing arm as they contested the ball near the hour mark of an otherwise one-sided contest.
Kylian Mbappe carelessness at the other end allowed Firmino to provide a thrilling climax to a pulsating night at Anfield to open Group C.
PSG got ready for next week's Champions League opener at Liverpool with a 4-0 win over Saint-Etienne at the Parc des Princes.
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