First-half goals from Edinson Cavani and Neymar, a second-half header from Marquinhos and a late Kylian Mbappe strike were enough to send Thomas Tuchel's side into the last 16, despite Marko Gobeljic's finish 56 minutes in.
The result, combined with Liverpool's 1-0 win over Napoli at Anfield, means PSG claimed top spot in its group, with Jurgen Klopp's side joining it in the last-16.
PSG took the lead nine minutes in, Mbappe bursting past Filip Stojkovic and squaring the ball for Cavani to tap in from six yards out.
Red Star responded well to the setback but only good saves from Milan Borjan stopped Mbappe and Neymar from adding a second goal before the half-hour mark.
There was no stopping Neymar from a dazzling finish five minutes before the break, the Brazil star collecting Mbappe's reverse pass, driving into the box and leaving Borjan on the ground with a dummy before firing home.
Red Star improved after half-time and deservedly got a goal back through Gobeljic, who volleyed expertly past Gianluigi Buffon at the near post, and the visitor looked to be unsettled for a time as the home fans roared their approval.
However, a fine free-kick from Angel Di Maria was powered into the net by an unmarked Marquinhos 16 minutes from time, and a clinical low strike from Mbappe in the closing seconds secured PSG's place in the next round as they ended a four-game winless run away from home in the competition.