The French giants were taking on Juventus at Le Parc des Princes when their star duo combined inside five minutes to give Christophe Galtier's side the lead in the most spectacular fashion.
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With Mbappe passing the ball in-field to Neymar, the Brazilian star pulled off a simply sublime chip to take five Juve defenders out of the equation and put it into the path of the 23-year-old.
Latching onto the pass in the area, Mbappe volleyed the ball low and hard past Mattia Perin into the bottom corner.
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It was like something straight out of FIFA.
Juventus are one of the top sides competing in the Champions League this season and for Neymar and Mbappe to dismantle them with one simple move merely highlights just how this PSG side can be if they work as a team.
Reports have emerged in recent weeks about a supposed rift between the two Paris Saint-Germain stars, something that Mbappe played down in the press, saying: "To talk about Neymar, this is the sixth year, I think we've always had a relationship like this based on respect," Mbappe told
"But we've always had moments like this where sometimes we've had moments that were a bit colder and moments that were a bit hotter.
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"There are times, you'll see, when we're the best of friends and sometimes we don't talk so much, it's the nature of our relationship that's like that."
Mbappe found the net again midway through the first half to double PSG's lead, before Weston McKennie got one back for Juve in the second half to set up a tense finale for the French side.
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However the combination play between their star duo was enough to see them get their Champions League campaign off to the best possible start.