Khvicha Kvaratskhelia opened the scoring after 20 minutes, powering a shot past Marco Bizot after gaining half a yard on Matty Cash, before 17-year-old Brian Madjo levelled for Aston Villa right on the stroke of half-time on his competitive debut, netting just days after being cleared to play following a dispute with FIFA over his registration.
PSG restored their lead in the 61st minute when Doué ran onto a pass from Ousmane Dembélé and curled a finish into the far corner, a goal initially flagged for offside before a VAR review showed Cash had played him onside.
Villa continued to threaten after the break, with a Matvey Safonov save from substitute George Hemmings and a last-ditch block by Warren Zaïre-Emery denying João Gomes an equaliser as PSG held on to become the first side since Real Madrid in 2016 and 2017 to win back-to-back Super Cups.
Unai Emery took pride in his side's performance despite the defeat.
"With a loss, you can never feel happy but how we compete, how the players respond on the field for 90 minutes, and our chances to score, we must feel really very proud of what we have done today," the Villa manager told TNT Sports.
He singled out his young forward and fellow debutant George Hemmings for praise.
"Their experiences and having days like today are very important. They show how are they are learning after their hard work. This is the way, we decided before the game how we wanted to play this game, we have worked the players in these positions."
Emery also explained the absence of Emiliano Martínez, Ezri Konsa and Ollie Watkins, who missed the match entirely.
"They are joining us after this match, we have our last friendly on Saturday. They are not going to be there but they will start training with us now, we wanted to give them four week holiday because the season was very demanding. We think it's better to work with players that are fit. Overall we can feel proud of everything we've done. Some changes will be needed but we are confident."
Asked whether further incomings could follow, Emery kept his answer brief: "Normally there will be more changes."
Villa playmaker Emiliano Buendía echoed his manager's mixed emotions.
"Not a good feeling. We can be proud of the game we did. We competed well. We had chances," he said. "They are top players. They get chances, they score and they won the game. We were there and competing very well [at 1-1]. At the end of the first half we had chances. Second half we were showing character."
Buendía also praised Madjo's contribution on his big night.
"I tried to help him. He's young. He has good development."
He added that Villa's overall approach would remain unchanged this season despite the summer's squad turnover: "There are changes but the structure, the manager and the club want to keep. We have to keep working hard."
For PSG, the win extended an already remarkable run under Luis Enrique, with the club now chasing as many as six trophies this season and a Trophée des Champions meeting against Lens to come on Sunday. Doué, who only returned to training on Monday following the World Cup, was delighted with his impact.
"This is amazing winning this trophy. It's really difficult because before that you have to win the Champions League again, and for the second time we have won the Super Cup," he said. "We are always hungry, we always want more. After the final in the Champions League, we wanted more, we have ambitions. We are a young team, and we want to win everything again this season."
Luis Enrique praised his squad's resilience given their disrupted pre-season.
"We knew prior to the game it was going to be a tough one. But we were able to play as we did because my players showed just what they're made of. We may not be in the best physical condition, but once again it's a real demonstration of our DNA and our fans, who have helped us to win trophies and keep standards high."