The contest marked Ronaldo's first outing in Saudi football since moving to the club earlier this month following his acrimonious exit from Manchester United, having seen his debut for Al-Nassr delayed by an existing ban from his time at Old Trafford.
The 37-year-old did not let the supporters down with two goals on the night, although it was his eternal rival Messi who ended up on the winning side having himself opened the scoring after only three minutes.
An action-packed contest saw four goals, a red card and two penalties in the first half alone, before five more goals arrived in the second half as PSG took the game away from their hosts, whose squad was made up of players plying their trade in the Saudi Pro League.
Despite seeing their Ligue 1 title bid harmed with defeat to Rennes just four days earlier, and an upcoming cup game on Monday, PSG boss Christophe Galtier named a strong starting lineup including the star attacking trident of Neymar, Messi and Kylian Mbappe - the latter two starting together for the first time since stealing the show in the World Cup final.
It took only three minutes for Messi to strike the first blow in what had been billed as the latest and perhaps last chapter in the storied Messi vs. Ronaldo rivalry, steering a finish past the onrushing keeper after Neymar's chipped ball through.
Ronaldo's first sight of goal saw him denied by Keylor Navas, whom reports have linked with a switch to join the Portuguese at Al-Nassr, and the two former Real Madrid teammates were involved again as the All-Star XI equalised.
A free kick into the box saw Navas clatter into Ronaldo, catching him with his forearm and leading the referee to point to the spot for a penalty which Ronaldo duly tucked away.
PSG were then reduced to 10 men when Juan Bernat was shown a straight red card for bringing down Salem Al Dawsari as the last man, with the referee ruling that he had denied a clear goalscoring opportunity despite the Saudi Arabia international, who memorably scored the winner against Messi's Argentina at the World Cup, being some way from goal.
However, the French champions were back ahead just four minutes later when Mbappe's cross into the box was flicked home by Marquinhos in the 43rd minute.
There was still plenty of time for more drama in the first half, though, as Neymar won a penalty following a challenge by Ali Al Bulayhi which was initially not given, only to be overturned when the referee went to the pitchside monitor.
The Brazilian's subsequent spot kick was dreadful, though, as the keeper comfortably saved to his left, and Ronaldo punished that by levelling things up in the sixth minute of first-half stoppage time.
The five-time Ballon d'Or winner's initial glancing header came back off the post, but his former Madrid teammate Sergio Ramos failed to clear his lines, allowing Ronaldo to slam home the rebound.
Ramos atoned for his error to restore PSG's lead eight minutes into the second half when he converted from close range following dizzying footwork from Mbappe, who beat his man three times down the left channel before picking out the Spaniard in the middle.
The hosts equalised again three minutes later through Jang Hyun-soo's glancing near-post header from a corner, but just three minutes after that PSG were back in front themselves, with Mbappe converting from the spot after Al Bulayhi blocked a Messi shot with his arm.
A raft of changes just past the hour mark saw Ronaldo, Messi, Neymar and Mbappe all taken off, and the action finally began to calm down after that.
However, there was still time for two more goals, with Hugo Ekitike effectively sealing the win for PSG 12 minutes from time when he was released through on goal before slamming home his finish, making Talisca's low stoppage-time drive from range a mere consolation for the Saudi XI.