Ander Herrera and Idrissa Gana Gueye also found the net for the capital side as they moved ominously on to nine points from a possible nine and clear at the top of the fledgling French table with a second consecutive 4-2 victory.
The full house of 15,000 in Brittany were denied the chance to see Messi make his PSG debut after the Argentine was left out of the squad as he continues to build up his fitness.
Neymar, who like Messi returned to training late after going all the way to the final of the Copa America last month, was also left out but PSG once again showed that they have little trouble finding the net and winning without the two superstars.
However, once again their defending left a lot to be desired and will have given coach Mauricio Pochettino food for thought with a number of players still waiting on the sidelines.
Donnarumma on the bench
Italy's Euro 2020 goalkeeping hero Gianluigi Donnarumma appeared in the squad for the first time since his arrival from AC Milan but was left on the bench as Keylor Navas started in goal.
Donnarumma's fellow European champion, Marco Verratti, did play for the first time this season in midfield but skipper Marquinhos was still missing.
Mbappe has dominated headlines in Paris ever since the arrival of Messi as speculation surrounds the future of the World Cup winner, who is out of contract at the end of the campaign and is a target for Real Madrid.
However he set up a total of four goals in the opening league wins against promoted Troyes and against Strasbourg, and once again Mbappe played a central role in the rudimentary surroundings of the Stade Francis-Le Ble.
PSG went ahead midway through the first half when Mbappe tried a clipped cross which was cleared out to the edge of the area where Herrera met the ball on the volley and the Spaniard's shot found the bottom corner.