“Neymar Jr, accompanied by his father and representative, communicated to FC Barcelona this morning his decision to leave the club,” Barca said in a statement.
“The club have informed them that the buyout clause in his contract that from July 1 is 222 million euros must be paid in full.”
Such a fee would smash the current record £89.3 million ($111 million, 105.2 million euros) Manchester United paid for Paul Pogba last year.
Neymar has also been given permission to not participate in training after making a brief appearance at Barca’s training ground on Wednesday.
Speculation over the 25-year-old’s future has dominated the first few weeks of new Barca boss Ernesto Valverde’s reign.
Neymar arrived back in Barcelona on Tuesday from a fleeting promotional tour to China.
He turned up for training at 9am local time (0700GMT) on Wednesday morning, but left less than an hour later after telling teammates “he is leaving”, a Barca spokesperson confirmed.
Presuming both clubs don’t come to a late agreement, the buyout clause would have to be paid to Barcelona via Spain’s La Liga to free the player from the contract he signed last year and runs until 2021.
However, La Liga president Javier Tebas has threatened not to accept PSG’s money over what he perceives as a failure on the French side’s part to comply with UEFA’s financial fair play rules (FFP).
Clubs can be sanctioned by UEFA for making a loss of more than 30 million euros over a three-year period.
“We will not accept this money from a club like PSG,” Tebas told Madrid sports daily AS on Wednesday.
“Especially when this club is infringing rules and laws.”
Barcelona have also threatened to report PSG to UEFA over any potential breach of FFP.
PSG have already been fined and saw their Champions League squad limited by UEFA for breaches of FFP in 2014.
– Champions League dream –
Winning the Champions League for a first time is the dream driving PSG’s owners Oryx Qatar Sports Investments (QSI) to fund a deal that could herald the start of a new era at the elite level of European football.
Since QSI’s takeover in 2011, PSG have failed to make it beyond the quarter-final stage in recent seasons – most notably blowing a 4-0 first leg lead to lose 6-1 to a Neymar-inspired Barcelona in the last 16 of last season’s competition in March.
Prising Neymar from the grip of Barca would truly announce PSG’s presence as a contender for the likes of Barca, Real Madrid and Bayern Munich to fear.
Neymar has formed one of the deadliest strike partnerships in football history with five-time World Player of the Year Lionel Messi and Luis Suarez over the past three seasons.
Together they have won two La Liga titles, a Champions League and three Spanish Cups, whilst Neymar has scored 105 goals and provided 80 assists in just 186 games.
Yet, one justification for Neymar to jump ship on top of the reported offer to triple his salary to 30 million euros net a season, is a desire to move out of Messi’s shadow if he is to end the Argentine and Cristiano Ronaldo’s decade-long dominance to win the Ballon d’Or.
Neymar’s four-year spell in Spain has also been overshadowed by the murky transfer deal which brought him to Barcelona from Santos in 2013.
He and his parents as well as Barca president Josep Maria Bartomeu face charges of fraud and corruption in an ongoing case brought by DIS, a Brazilian investment company.
DIS owned 40 percent of the players’ rights at the time of the deal and believe they were deliberately cheated out of their real share due to the complex structure of the transfer.
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