The right-back leaves the Dutch giants after six years at the Amsterdam ArenA, having penned a deal until 2016 to play in the French capital, where he will wear the No.23 jersey
The Dutchman's agent, Mino Raiola, had confirmed on Friday that a deal to take the French capital was nearing completion, but stressed that personal terms had not yet been agreed..
However, PSG have been able to finalise a deal for Van der Wiel, who will wear the No.23 shirt over the course of his stay at Parc des Princes.
The move also signals an end to the club's summer-long search for a right-back, as coach Carlo Ancelotti was keen to build on existing option Christophe Jallet.
Van der Wiel made his Ajax debut in 2007, and went onto make 137 appearances in all competitions for the reigning Dutch champions and has become Oranje's first choice in his position.
The transfer finally ends PSG's activity in the summer transfer market, with the Parisians having already signed the likes of Zlatan Ibrahimovic, Thiago Silva and Ezequiel Lavezzi.
Carlo Ancelotti's side ended a run of three straight draws on Sunday thanks to a 2-1 win at Lille, and now sit in ninth place in Ligue 1, six points behind leaders Olympique de Marseille.