The Brazilian, 25, missed training on Wednesday after telling teammates he wanted to leave the club, and was given permission by Barca manager Ernesto Valverde to take time off.
Barcelona later issued an official statement on the matter.
FC Barcelona communiqué on Neymar https://t.co/3gUqCGv5P8
— FC Barcelona (@FCBarcelona) August 2, 2017
“The player Neymar Jr, accompanied by his father and agent, has informed FC Barcelona this morning of his decision to leave the Club in a meeting held at the Club’s offices.”
He is expected in Paris later on Wednesday or on Thursday, to complete a medical and the signing of an expected €222 million ($260 million) transfer move.
The deal would eclipse the former world transfer record, set when Manchester United signed French midfielder Paul Pogba from Juventus for $116 million last summer.
Neymar has been at Barcelona since signing from Brazilian club Santos 2013 in a deal that ended up costing the Spanish club more than $100 million, according to club president Josep Maria Bartomeu.
He has scored 68 goals in over 100 appearances for the Catalan giants and won the Spanish La Liga title twice as well as the UEFA Champions League and FIFA Club World Cup titles.
He has also made 77 appearances for Brazil, scoring 52 times.
Speculation has mounted in recent weeks that he was on his way out of the Nou Camp, seemingly tempted by a hugely lucrative offer and the chance to lead the PSG line.
Neymar was at the heart of Barcelona’s famous Champions League comeback against PSG last season, when the Spanish giants overturned a four-goal first-leg deficit to win 6-1 at the Nou Camp and 6-5 on aggregate. He scored twice in that game and set up the winner, in a performance that will have done much to convince the French team to smash the world transfer record to sign him.
Neymar would also bring huge commercial value to PSG, with his almost 80 million Instagram followers and 30 million followers on Twitter.
PSG are bankrolled by their deep-pocketed Qatari owners, although some have questioned how the club could afford the deal without falling foul of Financial Fair Play regulations.
There are also reports that Barcelona will issue a complaint to UEFA over the transfer.
PSG insist that they are fully complaint with UEFA regulations, although there are suggestions they could sell players to make way for Neymar’s arrival.