Barcelona say Neymar can leave the Nou Camp but insist his buy-out clause of 222million euros (£198.5million) 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 euros, then worth £89m, that Manchester United paid Juventus for Paul Pogba last summer.
Neymar reportedly met with PSG chairman Nasser Al-Khelaifi in Qatar on Tuesday.
Lionel Messi wished his Barca team-mate of four years his best wishes after hearing the news.
The Argentinian posted on his Instagram account: "It was an enormous pleasure to have shared all these years with you friend @neymarjr I wish you good luck in this new stage of your life."
