The reigning European champions had to withstand several dangerous spells from their visitors before taking control through a series of outstanding finishes.
Desire Doue opened the scoring in the 38th minute after PSG punished Barcelona's attempt to build from the back. The forward intercepted possession before driving towards the penalty area and firing into the bottom-left corner, continuing his excellent form following last week's win over Manchester City.
Barcelona responded around 10 minutes into the second half when teenage defender Xavi Espart burst into the box and beat Matvey Safonov at his near post. The visitors subsequently threatened to take the lead, with Ferran Torres striking the woodwork on a swift counter-attack.
Lucas Hernandez restored PSG's advantage with a powerful header from a corner, but Lamine Yamal produced a moment of individual brilliance to make it 2-2. The Barcelona forward turned Warren Zaire-Emery before accelerating into the area and squeezing his shot past Safonov.
PSG's response was immediate. Less than two minutes later, Vitinha controlled a clearance on his chest before unleashing a superb volley into the bottom corner.
Fabian Ruiz then completed the scoring five minutes afterwards, converting Achraf Hakimi's low delivery at the far post.
Both goalkeepers had important contributions during an encounter filled with chances. Joan Garcia denied Doue and Ousmane Dembele in the opening period, while Safonov thwarted Fermin Lopez in a one-on-one situation shortly before half-time.
"I think we witnessed two teams playing incredible football, such attacking football. We showed our level. It was a very competitive match," said PSG boss Luis Enrique.
"It was hard to keep control of the game. It's only three more points, but it's always positive to defeat such a quality side. The players that came off the bench were excellent and gave us a real boost. We are very happy."
The result leaves PSG on nine points in the Champions League, with a trip to Villarreal awaiting them on Tuesday, 3 November. Barcelona remain on six points and will welcome Aston Villa to Camp Nou on the same evening.
Jose Mourinho has praised Real Madrid's squad depth after their 4-1 Champions League win over RB Leipzig but insisted his team must improve before Sunday's El Clásico against FC Barcelona.
Youri Tielemans admitted Manchester United were lacking in every department after their shocking 4-1 Champions League defeat to Como in Italy on Wednesday, which extended their winless run to seven matches.
Barcelona midfielder Dani Olmo will miss Sunday's El Clasico against Real Madrid after suffering a thigh injury during Tuesday's 4-2 Champions League defeat by Paris Saint-Germain.
Manchester United endured a humiliating European evening against Como, suffering a comprehensive 4-1 defeat that intensified the scrutiny surrounding manager Michael Carrick.
