Andre finished off a delightful move in the 86th minute to send the Dragao stadium into raptures as Porto gave coach Julen Lopetegui his first win, and first goal, against Benfica since he took over at the start of last season.
Porto, who have seen Benfica walk off with the title in the last two seasons, were also indebted to former Real Madrid goalkeeper Iker Casillas who made two outstanding saves to stop the champions taking an early lead.
Porto's win left them top with 13 points from five games, three ahead of Sporting, who host Nacional on Monday. Benfica, whose new coach Rui Vitoria is already under pressure, are third with nine.
Kostas Mitroglou had the first chance for Benfica when his header was brilliantly saved by Casillas who then made an equally good stop to block Luisao's header from a corner as the visitors looked dangerous.
There were plenty of heavy challenges and Porto full back Maxi Pereira, who left Benfica after eight campaigns to join their arch-rivals during the close season, was in the thick of the action.
The Uruguayan was one of eight players booked as the challenges flew in thick and fast.
Porto defender Maicon aimed a wild karate kick at Jonas at the end of the first half and, although there was no contact, it led to a skirmish involved a dozen players.
Porto's Vincent Aboubakar headed against the post and then forced a last-gasp saved from Julio Cesar as the hosts took control after halftime.
The home crowd reacted angrily when the Cameroon forward was replaced by Pablo Dani Osvaldo but were quickly placated by Andre's goal four minutes from time.
Silvestre Varela cleverly backheeled the ball into Andre's path and he made no mistake as he beat Julio Cesar from the edge of the area for his first goal since joining Porto from Vitoria Guimaraes in the close season.
(Writing by Brian Homewood; Editing by Ken Ferris)
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