PSG's audacious pursuit of Barcelona superstar Neymar has been dominating the headlines in recent weeks, but it was Brazil team-mate Alves, signed on a free transfer from Juventus, that announced himself to the club's faithful in stunning fashion in Saturday's curtain raiser in Morocco.
The evergreen 34-year-old, playing in the unfamiliar position on the right of a front-three, blasted in a long-range free-kick shortly after the restart to cancel out Djibril Sidibe's expertly taken first-half opener.
And Alves' brilliant cross was headed home by Adrien Rabiot just after the hour to secure PSG a fifth consecutive Trophee des Champions victory.
The result puts into focus the challenge Monaco, who saw late penalty claims for handball against Rabiot dismissed, face in defending their shock Ligue 1 title victory this season.
Leonardo Jardim's men swashbuckled their way to the championship last term, but have lost Benjamin Mendy, Bernardo Silva and Tiemoue Bakayoko during the close-season, while the jewel in their attacking crown Kylian Mbappe is being heavily linked with a €180million move to Real Madrid.
PSG coach Unai Emery will be fully aware that the pressure is on this season to at a minimum regain the Ligue 1 title, but, with or without Neymar, they appear fully equipped to do just that.
Mbappe was impressive throughout for Monaco and the France forward had the ball in the back of the net in the fifth minute, but the goal was rightly ruled offside.
At the other end, Rabiot combined with Layvin Kurzawa before teeing up Alves, whose half-volley Danijel Subasic spilled before the Monaco goalkeeper recovered to deny Edinson Cavani.
The lively nature of the match continued and Jemerson made a superb block to deny Cavani sweeping in Kurzawa's centre at the end of a lightning PSG break.
PSG began to stamp their authority on the match, but their failure to take advantage proved costly as Monaco opened the scoring with a fine breakaway goal on the half hour.
Monaco gained possession in PSG territory and debutant Youri Tielemans' exquisite throughball was collected by Sidibe, who provided an equally brilliant dink over Alphonse Areola.
Radamel Falcao had the opportunity to double the lead when he met Sidibe's teasing right-wing cross with a powerful header that cleared the crossbar.
But PSG were level in stunning fashion in the 51st minute when Alves smashed in a 30-yard free-kick to the left of Subasic that barely span as it nestled in the goal.
Rabiot then muscled in front of Kamil Glik to head wide from an Alves centre, but the same combination proved more fruitful in the 63rd minute.
Javier Pastore released Alves on the right of the box and he hung up a perfect cross for Rabiot to hammer his header past Subasic.
PSG were grateful to Areola for making a low save down to his right to keep out Guido Carrillo's powerful downward header, while Thiago Silva made a fine block from Thomas Lemar's follow-up.
Monaco had late claims for a penalty waved away when Rabiot seemingly controlled a Lemar cross with his arm, but Emery's men withstood a late surge to once again begin their season with silverware.