The 25-year-old donned a white t-shirt and a black and white baseball cap and was flanked by his father Neymar Sr, who brokered the deal.
Alongside agent Wagner Ribeiro, the Brazilian has been in the pipeline to join PSG all summer, but last night the Ligue 1 giants confirmed their capture.
PSG’s store started selling shirts with “Neymar Jr 10” on the back for £140 each as fans posed with the jerseys.
Meanwhile in Brittany, fans of Ligue 1 club Guingamp were queuing around the block to get tickets for their clash with PSG in the club’s second fixture of the season.
He will complete his switch to Parc-des-Princes after the French club activated his release clause of £198m, which has been confirmed as a Guinness World Record.
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Neymar has already signed a five-year deal at the club worth a whopping £515,000-a-week.
His father and agent were at his side as he put pen to paper on the contract and made history.
Angry Barcelona fans even burned shirts with his name on the back, as they were so incensed by the switch.
Neymar has allegedly become fed up of playing in the shadow of Lionel Messi at Barcelona and wants to make a tilt for the Ballon d’Or in his own right.
In an emotional post on Instagram, Neymar explained why he wanted to make the move.
He said: “I am sure I will never see another one like him while I’m alive. Leo Messi became my friend on and off the pitch. It was an honour to play with you.
“I made a trio with Messi and Suarez that made history, conquered everything an athlete can conquer, lived unforgettable moments, lived in a city that is more than a city, it is a homeland.
“I love Barcelona and Catalonia.”
Neymar will be unveiled on this afternoon in the French capital and again before the Ligue 1 clash with Amiens on Saturday.
He said his father, Neymar Sr, wanted him to stay at Barcelona but he will earn £40.7m a year on a five-year deal.
He said: “I have won all that a player can win.”