Former Rangers man stamps his claim for a first-team spot down with a superb treble but the star of the night was the veteran full-back, who scored his first goal for the Toffees
The former Rangers man offered a signal of his intent to the Goodison Park faithful as David Moyes fielded a strong squad to reflect Hibbert's determination to win as summer signing Steven Pienaar also made his Blues bow following his re-signing from Tottenham last week.
The duo combined brilliantly in the first minute as Pienaar threaded the ball to Naismith, who was able to beat the Greek club's offside trap before hoisting the ball over Dimitris Konstantopoulos and into an empty net to give Hibbert the start he would have hoped for.
But the advantage was short-lived as AEK Athens responded with an impressive volley from Taxiarchis Fountas, who unleashed a fierce right-footed shot past a sprawling Tim Howard.
Everton, however, had the combination of Pienaar and Naismith to thank for retaking the lead as the South African fired a pinpoint cross for the Scotland international to head home comfortably.
Any suggestions that Nikica Jelavic would be the ideal fold for his former Ibrox partner in crime appear to be misinformed if his understanding with Pienaar continue to flourish.
Hibbert, captaining his boyhood club for the first time, was regularly urged by the home crowd to "shoot!" and when he did, he set the wheels in motion for Everton's third as he forced a fingertip save from Konstantopoulos. The ensuing corner from Pienaar found Marouane Fellaini, whose crashed effort against the crossbar was pounced on by a predatory Naismith.
Already the attacker's free transfer from the beleaguered Rangers looks to be one of the finest pieces of business conducted in the summer transfer window. Similiarly the long-term deal agreed for his namesake appears an equally astute piece of business.
Moyes rang the changes after the interval with match winner Naismith replaced by Seamus Coleman while Howard and Fellaini were both withdrawn in favour of Jan Mucha and Magaye Gueye respectively as Everton's high-tempo first half was matched in the second. Mucha's only real test came in the final third when substitutes Valentinos Viachos and Nikolaos Kourelas both drove low efforts but neither troubled the Blues' stand-in goalkeeper.
The home crowd have long vowed that they would riot if Hibbert did score and they stayed true to their word as the veteran defender rifled home a free kick from just outside the area to prompt a pitch invasion of nostalgic proportions.
Few anticipated it would happen, such is the right-back's insistence on winning every game at all costs, but they were determined to make the most of what proved to be a remarkable night at Goodison.