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Centre-back Pique has been out since November with a knee ligament injury but Barca coach Ronald Koeman decided to gamble on the 34-year-old, who returned to training this week ahead of the first leg.
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Lionel Messi also started in a front three alongside Antoine Griezmann and Ousmane Dembele, with the in-form Frenkie de Jong back in midfield after filling in as a centre back in recent weeks.
PSG was boosted by the return of Marco Verratti, who was passed fit to start despite missing last weekend’s win over Nice with a hip problem.
Neymar and Angel Di Maria were both ruled out injured for Mauricio Pochettino’s side, meaning Moise Kean joined Verratti and Kylian Mbappe behind Mauro Icardi at Camp Nou.
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Barcelona (4-3-3)
Marc-Andre ter Stegen, Sergino Dest, Gerard Pique, Clement Lenglet, Jordi Alba; Sergio Busquets, Frenkie de Jong, Pedri; Lionel Messi, Antoine Griezmann, Ousmane Dembele
Coach: Ronald Koeman (NED)
Paris Saint-Germain (4-2-3-1)
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Keylor Navas, Alessandro Florenzi, Marquinhos, Presnel Kimpembe, Layvin Kurzawa; Idrissa Gueye, Leandro Paredes; Moise Kean, Marco Verratti, Kylian Mbappe; Mauro Icardi
Coach: Mauricio Pochettino (ARG)
Referee: Bjorn Kuipers (NED)
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