The Ligue 1 champions announced a deal had been reached with the Premier League outfit last month and it has been confirmed that the 27-year-old centre-back will be under contract at the Parc des Princes until at least 2019.
Luiz is currently on FIFA World Cup duty with Brazil and will join up with Laurent Blanc's side after the tournament.
A statement on PSG's official website read: "Paris Saint-Germain is pleased to announce that Brazil international David Luiz will join from Chelsea for a period of five years.
"He will join the group at the end of the World Cup where he is playing with the Selecao."
Luiz made the switch to Stamford Bridge in January 2011 in a reported €25 million deal from Primeira Liga champions Benfica.
His time with the London club has brought success in continental competitions in the shape of the UEFA Champions League and Europa League, as well as FA Cup success in 2012.
However, the defender fell out of favour under Jose Mourinho and he was restricted to just 15 Premier League starts last season.
The move to PSG will see him link up with fellow centre-back and Brazil team-mate Thiago Silva, and comes just a day after Chelsea completed a deal to sign Barcelona midfielder Cesc Fabregas on a five-year contract.
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