The Argentina winger was banned for four matches for spitting at Marseille defender Alvaro during an ugly Classique and last featured in France's top flight against Reims on 28 September (AEDT).
But it was his pressing that forced the error from which Moise Kean scored his third Ligue 1 goal and Di Maria added a second after 20 minutes with an audacious chip.
Di Maria added somewhat unfair gloss in the second half as PSG provided a good riposte to a damaging 2-1 reverse against RB Leipzig in the UEFA Champions League, although Kean was one of four enforced subs for Thomas Tuchel as the PSG coach's injury list lengthened.
Rennes mixed bright play with careless passing early on and it was from one such lax interchange between goalkeeper Alfred Gomis and James Lea Siliki that Di Maria toed into the path of Kean, who drilled expertly into the bottom-left corner.
Only the post denied Di Maria's excellent long-ranger on the half-volley but the awesome Argentinean doubled the lead with a sumptuous piece of skill after collecting Ander Herrera's throughball.
Steven N'Zonzi's aerial prowess caused a couple of nervy moments, while Kean put a free header over the top himself.
PSG did not show a great deal of adventure, but the fact Kean limped off in the 61st minute after Idrissa Gueye, Thilo Kehrer and Alessandro Florenzi had already been subbed perhaps explained a more measured approach.
Instead, Rennes asked more second-half questions without ever troubling its opposition, handball claims against Leandro Parades and Danilo Pereira from the same Hamari Traore cross not interesting the VAR (video assistant referee).
But it was game over when Di Maria drifted in from the right and picked out the far corner with a deflected daisy-cutter in the 73rd minute to cap a fine outing.