The club released an official statement on Thursday that read: "On Thursday afternoon Neymar Jr's legal representatives visited in person the club's offices and made the payment of €222m in the player's name with regards to the unilateral termination of the contract that united both parties.
"As such, the club will pass on to UEFA the details of the above operation so that they can determine the disciplinary responsibilities that may arise from this case."
Earlier on Thursday, La Liga refused to accept an attempt to pay the release clause at their offices in Madrid , leading to France's Ligue de Football Professionnel to call on the Spanish body to "abide by the rules of FIFA and its responsibilities".
FC Barcelona communiqué on Neymar Jr https://t.co/G87wtAhVxe— FC Barcelona (@FCBarcelona) August 3, 2017
Neymar's move to PSG now looks set to be completed imminently, with the Ligue 1 side reportedly ready to unveil the Brazilian on Friday.
Barca president Josep Maria Bartomeu has previously suggested PSG's move for Neymar would not be possible without contravening UEFAs' Financial Fair Play (FFP) regulations.
It is understood UEFA will investigate the deal if it suspects that there has been any breach of FFP rules.
La Liga president Javier Tebas has also threatened to report PSG to UEFA over the deal , which will set a new world-record transfer, smashing the previous record set by Paul Pogba's €105m move from Juventus to Manchester United a year ago.
Neymar has reportedly already undergone a medical in Porto, and it is believed he will travel to the French capital to finalise the deal on Friday.