The 25-year-old Brazil forward, who will be presented to fans on Saturday, is committed to PSG until June 2022, the club said in a statement. Media reports have said he could earn around 550,000 euros per week.
"Today, with the arrival of Neymar Jr, I am convinced that we will come even closer, with the support of our faithful fans, to realising our greatest dreams,” said PSG's Qatari President Nasser Al-Khelaifi.
Both Barcelona and Spain's La Liga questioned whether the move complied with UEFA's financial regulations, with the club saying they would report the deal to European football's governing body.
The transfer doubles the previous world record fee paid when Paul Pogba moved last August from Juventus to Manchester United for a 105 million euros.
With the Spanish giants certain to be in the market for a replacement for the Brazilian forward - and with a hefty budget to invest - the Neymar move could set off a chain reaction of deals at top clubs across Europe.
Yet for PSG the signing is a huge coup, bringing them one of the most exciting talents in the world game.
Gifted with a superb touch and an impressive repertoire of tricks, Neymar was part of one of the most devastating strike trios the game has ever seen, playing at Barcelona alongside Lionel Messi and Luis Suarez.
In four years in Catalonia, he won the Champions League once, La Liga twice, and the King's Cup three times.
The focal point of the Brazil national team, who will be aiming for a record sixth World Cup title in Russia next year, Neymar's popularity soared after he captained his country to their first Olympic gold medal in Rio last year -- scoring a brilliant free kick and the deciding penalty in the final.
NEW HORIZONS
Neymar, who also has lucrative endorsement deals with Nike, Gillette, Panasonic and Beats by Dre, said he was looking forward to delivering trophies for the French club.
"I am extremely happy to join Paris St Germain," he said in the club's statement.
"Since I arrived in Europe, the club has always been one of the most competitive and most ambitious. And the biggest challenge, what most motivated me to join my new team mates is to help the club to conquer the titles that their fans want.
"From today, I will do everything I can to help my new team mates, to open up new horizons for my club and to bring happiness to its millions of supporters around the world," he said.
The excitement was certainly felt by PSG fans. Several hundred gathered outside the palatial Royal Monceau hotel in the capital, letting off flares and breaking into chants.
Barcelona said in a statement on their website (www.barcelona.com) that Neymar's legal representatives "visited in person the club's offices and made the payment of 222 million euros..."
The five-times European champions said they would pass on details of the operation to European soccer body UEFA "so that they can determine the disciplinary responsibilities that may arise from this case."
Barcelona did not specify why they believed there may be a disciplinary issue relating to the deal. Javier Tebas, head of La Liga had earlier said that PSG were engaged in "financial doping" and the Spanish body would also complain to UEFA.
Tebas referred to PSG, who are owned by Qatari Sports Investments, as a "state backed club".
UEFA, whose financial fair play rules ban clubs from spending more than their generated revenue, declined to comment but a spokesman noted that international transfers are within the remit of global governing body FIFA.
A source from Spain's La Liga said earlier on Thursday that the league had rejected the payment of the clause to them after Neymar's lawyers visited its headquarters in Madrid to try to settle the transfer and pay the fee.
(Writing by Simon Evans; Additional reporting by Martyn Herman, Brian Homewood, Sarah White and Michael Gore; Editing by Toby Davis)
