In a statement released today, Barcelona says that "Neymar Jr's legal representatives visited in person the club's offices and made the payment of 222 million euros in the player's name with regards to the unilateral termination of the contract that united both parties."
There was no immediate confirmation of a transfer by PSG.
The payment of the clause shatters the previous world record transfer of 105 million euros (then USD 116 million) that Manchester United paid for France midfielder Paul Pogba last year.
The comment follows a claim by Spanish league president Javier Tebas yesterday that Neymar's move would break Financial Fair Play rules introduced by UEFA, European soccer's ruling body.
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Barcelona did all it could to stop Neymar from leaving, and had vowed to complain to UEFA if his seemingly untouchable release clause was triggered.
The payment of the clause directly to the club was the second attempt Neymar's representatives had made today to break his bond with Barcelona.
Tebas had told Spanish sports daily AS that he wouldn't let the league act as an intermediary to an operation that he, like Barcelona, believed violated UEFA's FFP rules. He had called PSG a "state-supported club." The club's Qatari owners are closely linked to the energy-rich ruling family. Neymar ended weeks of silence by telling Barcelona's executives, players and coach on Wednesday that his intention was to leave the club after four seasons.
At 25 years old, Neymar is already one of soccer's top talents.
Neymar scored 105 goals playing alongside Lionel Messi and was a key playmaker for Barcelona as it won a Champions League, two Spanish leagues, three Copa del Reys, one Club World Cup, a UEFA Super Cup and two Spanish Super Cups.
The expectation at PSG will be for him to lead it to elusive Champions League success.