Barcelona have given Neymar permission to discuss a move away from the club but will insist his buy-out clause of €222m is paid in full.
The Brazil forward, heavily linked with a move to Paris St Germain, made a brief visit to Barca's training ground on Wednesday to inform them of his wish to leave the club, departing before their training session began.
A club statement read: "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.
"Faced with this position, the club has informed them they refer to the buy-out clause of his existing contract which as of 1 July totals 222million euros, which will have to be deposited in its entirety.
"Furthermore, in reply to the claim for the contract extension bonus, the club has once again made it clear that the amount remains deposited with a notary until the case is resolved.
"The player remains under contract at FC Barcelona but with temporary permission to not take part in training sessions."
The former Santos player has a contract with Barca until 2021 but PSG, deposed by Monaco as French champions last term, appear prepared to activate his release clause.
That would more than double the existing world record fee of €105m, that Manchester United paid Juventus for Paul Pogba last summer.
In his three seasons in Catalunya, Neymar has helped Barca win LaLiga twice, the Champions League once, the Copa del Rey on three occasions and the FIFA Club World Cup.
Neymar reportedly met with PSG chairman Nasser Al-Khelaifi in Qatar on Tuesday.
Al-Khelaifi was giving nothing away during an interview with Moroccan broadcaster Medi 1 TV over the weekend.
In quotes reported by various European news outlets on Tuesday, Al-Khelaifi said: "Right now, Neymar is a Barcelona player and we'll see what happens with him.
"We respect all contracts signed with other clubs and players.
"To be honest, I'd rather not to talk about this matter now. I hope to do it at another time."
The unprecedented scale of the deal has sparked rumours that Barca could make a complaint to UEFA over a purported failure to adhere to Financial Fair Play rules by the purchasing club.
UEFA has said it has not received a complaint but would look into the details of the transfer if it goes ahead.
PSG's squad contains four players who have played with Neymar for Brazil, with Dani Alves - also a former team-mate at Barcelona - having already joined the club this summer.