The Brazilian had been continually linked with a move away from Camp Nou over the summer, and had declined to clarify his own future as the PSG rumours grew stronger.
And after weeks of denials, mixed messages and reports, he has finally been confirmed as the Ligue 1 club's latest signing on Thursday night.
"Paris Saint-Germain are very pleased to announce the arrival of Neymar Jr," the Parisiens said in a statement on their official website.
"The Brazilian attacker signed a five-year contract in the presence of club and player representatives. Neymar Jr is now tied to the club of the capital until June 30, 2022."
Earlier on Thursday, La Liga attempted to derail the deal by refusing to accept the €222m payment from Neymar's lawyer, but his representatives paid direct to Barcelona instead.
In the late afternoon Barcelona confirmed they had accepted the bid and a transfer of a player they bought four years ago looked certain.
NEYMAR THE NEW WORLD RECORD HOLDER
The fee, equivalent to Neymar's buyout clause, shatters the existing record of €105m, set last year by Paul Pogba.
Neymar emerged as a teenage wonderkid at Santos, winning the Copa Libertadores in 2011 before switching Brazil for Catalunya.
After moving to Camp Nou in 2013 the Brazilian hit 105 goals in 186 games for Barca, forming part of the formidable MSN forward line alongside Luis Suarez and Lionel Messi.
Having gone trophyless in his debut season Neymar celebrated the treble in 2014-15, adding a further Liga and two Copa del Rey trophies in the following two campaigns as well as a host of other team and individual titles.