The French champions had been accused of lacking a cutting edge after drawing six of their first nine matches in all competitions and a Group F defeat against Barca at the Parc des Princes would have piled the pressure on coach Laurent Blanc.
Although they were deprived of the talismanic Zlatan Ibrahimovic, ruled out with a heel injury, big-spending PSG were back to their exuberant best as they romped to a 3-2 win on an electric Parisian night.
"It's true that the Champions League gives the players extra motivation," Blanc admitted as his side's early aggression was rewarded with David Luiz's opener in the 10th minute.
Marco Verratti and Blaise Matuidi also found the back of the net while Barca, who had not conceded a goal all season, scored twice through Lionel Messi and Neymar.
"The difference with the other games is that we were more aggressive," goalkeeper Salvatore Sirigu said.
It was about time, according to Blanc, who also had to contend with the absence of the injured Thiago Silva and Ezequiel Lavezzi.
"We were going through a rough patch even if we had not lost a game," the former Barca centre back said.
"We needed a high collective performance. We needed a game like this. After such a night, either you have the solution or you find yourself at the bottom of the hole.
"We eventually discovered a nice team."
PSG lead Group F on four points from two games with Barca second on three. Ajax Amsterdam are third on two points after drawing 1-1 at APOEL, who have one point.
"It is going to give us confidence," fullback Maxwell added.
"It is true that we went through a difficult time and we needed that confidence boost," said club president Nasser al-Khelaifi, who went as far as describing the win as his "best victory with PSG".
"I think it's the start of our season. I hope we are going to continue like this."
On Sunday, PSG will have an opportunity to show the victory was not just a flash in the pan when they host last year's Ligue 1 runners-up Monaco in a another high-profile game at the Parc des Princes.
"I hope we will be able to show the same intensity in other games," Sirigu added.
(Editing by John O'Brien)
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