Barca confirmed on Wednesday that the 25-year-old had requested and been granted permission to miss training in order to finalise his transfer.
The deal will be completed this week, his agent, Wagner Ribeiro, says as the move gained a great deal of momentum upon his return from a promotional tour in China.
Neymar had stayed quiet through all the reports and even featured for Barcelona in the International Champions Cup in the United States, impressing in wins over Juventus, Manchester United and Real Madrid as Ernesto Valverde's side won the competition.
However, the offer from PSG seems to have been too great to pass up and he is to be named a PSG player by the end of the week. Here, Goal takes a look at the key details behind the shock summer transfer...
HOW MUCH WILL NEYMAR EARN AT PSG?
Neymar is expected to earn €30 million per year at Paris Saint-Germain after tax once the move from Barcelona is confirmed, having signed a new contract with the Catalan club only last year.
It has also been reported in Spain that the player's father will receive a payment of around €40 million if his son completes a transfer to PSG.
HOW MUCH WILL PSG PAY BARCELONA?
Neymar's release clause stands at €222 million and that is how much Paris Saint-Germain will have to pay in order to sign the Brazil forward this summer.
After announcing he had asked to leave, Barca reiterated that his clause would have to be paid in full for him to leave.
"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 222 million euros which will have to be deposited in its entirety," a statement read.
"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."
Ribeiro has said PSG will pay the required fee, but it could be that Neymar will pay the clause himself and be reimbursed by the French side, as Barca do not want to negotiate with them for his transfer.
That means PSG will also have to pay tax on the transfer, with somewhere between €100m and €120m to be deposited with the French authorities.
WHY IS NEYMAR SIGNING FOR PSG?
Neymar arrived at Barcelona from Santos as a global star in 2013, but the Brazilian forward has always been overshadowed by Lionel Messi at Camp Nou and he is keen to be the main man for one of Europe's elite clubs.
At Barca, that would mean waiting for several more years because Messi is still at a phenomenal level. At PSG, he will be the team's star player and also the focal point in an ambitious sporting project.
The 25-year-old wants to win the Ballon d'Or and at his current club, he is in the shadow not only of Messi, but also Real Madrid's Cristiano Ronaldo, so a move to PSG would give him a better chance to stand out - especially if he can help the Parisian side to win the Champions League.
Money may also be a motivation, with the player's father believed to be pushing for a deal in order to earn more millions with a big bonus once the move is completed.
WHAT IS NEYMAR'S CONTRACT LENGTH?
Neymar will sign a five-year deal at PSG providing the transfer is completed. That will see the Brazilian tied to the French side until 2022, when he will turn 30.
WHO COULD REPLACE NEYMAR AT BARCELONA?
Barcelona are keen on Philippe Coutinho, having hoped to sign the Liverpool midfielder as a team-mate for Neymar, not as his replacement. The Catalan club remain interested in the Brazilian - even though Reds boss Jurgen Klopp claims he is not for sale.
Antoine Griezmann has also been linked with a move to Camp Nou, but the France forward pledged his future to Atletico Madrid earlier on this summer and is extremely unlikely to go back on that promise this summer.
Juventus forward Paulo Dybala is another alternative, along with Borussia Dortmund winger Ousmane Dembele, with Real Madrid target Kylian Mbappe also linked along with PSG's very own Angel Di Maria.