Blaugrana head coach Xavi has confirmed that the French champions have offered Dembele a financial package that they cannot compete with, and the 26-year-old will soon be returning to his homeland.
Dembele became a free agent for a couple of weeks last year before ultimately agreeing to a two-year Barca extension, which contained a €50m (£43.1m) release clause.
That option recently doubled in size to €100m (£86.2m), but Barcelona were previously in discussions with the former Borussia Dortmund man over a long-term renewal.
However, PSG apparently activated a secret clause in Dembele's Blaugrana contract, and the capital giants have now reached a full agreement to sign the attacker.
A report from RMC Sport states that Dembele touched down in Paris on Thursday, and the France international will complete his medical examinations on Friday before penning a five-year deal.
Dembele leaves Barcelona following a mixed and injury-hit six-year spell, having commanded a mammoth fee of €140m (£120.6m) to leave Dortmund in the summer of 2017.
The ex-Rennes youngster scored 40 goals and set up 43 more in 185 games for La Blaugrana, including eight strikes and nine assists from 35 matches in all tournaments during the 2022-23 season.
Dembele won three La Liga titles in addition to two Copa del Reys and two Supercopa de Espana titles at Camp Nou, but he missed a further 119 matches due to a plethora of physical problems.
Should all go to plan in the coming hours, Dembele will become PSG's ninth signing of a busy summer window, following Milan Skriniar, Marco Asensio, Manuel Ugarte, Xavi Simons, Lucas Hernandez, Lee Kang-in, Cher Ndour and Arnau Tenas to the Parc des Princes.
Despite their lucrative summer spending, PSG are still active in the market and are now expected to turn their attention to a deal for Benfica striker Goncalo Ramos.
A deal worth up to €80m (£68.9m) has supposedly been agreed between the two clubs, which will see PSG pay €65m (£56m) upfront with a further €15m (£12.9m) in performance-related add-ons.
The French champions have lost Lionel Messi and Mauro Icardi from their attacking ranks this summer, while the Kylian Mbappe saga continues to provide an unwelcome distraction to Enrique.
PSG are trying to force the attacker out of the door after he informed them that he would not be extending his contract beyond 2024, but only Al-Hilal have shown a willingness to meet Les Parisiens' asking price, and Mbappe refused to enter talks with the Saudi Arabian club.
A shock loan move to Liverpool was mooted before Jurgen Klopp rubbished such claims, but Mbappe would supposedly be open to a short-term switch to Chelsea.