The much anticipated move was announced just a day after Cavani arrived in Paris to finalize the deal.
The 26-year-old Napoli forward, who was Serie A top scorer last season with 29 goals, landed in Paris on Monday morning before heading to a top city hotel.
Late morning, outgoing PSG sporting director Leonardo was seen leaving the luxury hotel with an advisor of the Uruguay player, who is nicknamed "The Matador".
Cavani had to pass a medical before putting pen to paper. He is believed to have signed a 5-year contract.
He will line up alongside his former Napoli team-mate Ezequiel Lavezzi, of Argentina.
The previous French Ligue 1 transfer record was set earlier this year, when Colombia forward Radamel Falcao signed for Monaco from Atletico Madrid for a figure estimated at nearly 60 million euros.
PSG meanwhile sought to silence rumours that have been flying in the Catalan sporting press since last week about a possible departure of the Brazil central defender Thiago Silva to Barcelona.
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Silva's agent, Paulo Tonieto, was quoted as saying on PSG's official website: "Thiago is a PSG player. He has a contract and he will respect it.
"The rumours are the same as the ones last year but Thiago Silva is a PSG player and he'll see out his conttract with his club."