He is joined by former Clifford Chance partners Danny Simmons and Joni Henry.
The hires follow that of former Gilbert+Tobin, DLA Piper and legacy Phillips Fox chief Tony Holland; and Paul Saward and Andrew Farr. All three joined in August.
Pistilli and Simmons left Clifford Chance in April this year and launched law firm Pistilli Simmons in May.
Pistilli was also founding partner of Chang, Pistilli & Simmons (CP&S) which merged with Clifford Chance in 2011. As well as being the first managing partner of the Sydney office of Clifford Chance, he was a member of its Asian Leadership Group and a joint global head of the mining group.
The legal arm of PwC was started two years ago by former King & Wood Mallesons managing partners Tony O'Malley and Tim Blue.
Mark Pistilli, the co-founder and former managing partner of Clifford Chance Australia has joined PwC Legal just months after launching a boutique firm in Sydney.