In 2023 Djokovic won, as he did in January's Australian Open semi, while last year Sinner triumphed.
Both completed tricky second-round matches in straight sets on Wednesday (Thursday AEST), dismissing Nuno Borges and Stefanos Tsitsipas respectively.
Sinner needed two tiebreaks and laboured at times, but rarely looked in danger as he won 7-6 (7-4) 7-6 (7-2) 6-4.
World No.48 Borges provided stubborn resistance and was a point away from taking the second set, but Sinner was rock-solid when it mattered.
He did drop serve early in the second set, but having held the advantage to 5-4 Portugal's Borges buried a routine backhand into the net on set point and paid the price as Sinner broke back and then reeled off six points in a row to win the breaker.
Afterwards he admitted that maybe going straight from the clay of Roland Garros, where he suffered a shock second-round defeat, the Wimbledon grass was ill-advised and next year he might play at Queen's.
As he had at the 2021 French Open and 2023 Australian Open finals, Djokovic beat Tsitsipas, this time 6-3 6-4 6-2 in less than 100 minutes.
Tsitsipas is now free of the lingering back trouble that sped his plummet down the rankings to No.87, but to the disappointment of a Centre Court crowd craving some drama was still unable to best, or even trouble, the 39-year-old Serb against whom he now has a 2-13 record.
"Obviously you feel very satisfied and joyful on the court when you're playing this way," said Djokovic.
"I feel great, I try not to take these moments for granted. I feel very privileged to be walking out on the court at age 30 plus. I actually believe it's true, age is just a number."
Maybe third seed Auger-Aliassime, now showing signs of making good on his potential, will test a man 14 years his senior. The Canadian eased past Croatia's Dino Prizmic 7-6 (7-2) 6-3 7-5.
Auger-Aliassime and Djokovic have met twice, with a win apiece, but never on grass.
Eighth seed Daniil Medvedev enjoyed a four-set win against Spain's Daniel Merida, French Open runner-up Flavio Cobolli, seeded nine, beat Mariano Navone to set up a meeting with Australia's James Duckworth and Brazilian teenager Joao Fonseca was roared on by his yellow-clad fan club as he blazed past Jesper de Jong.
Francis Tiafoe, seeded 17, progressed, defeating Terence Atmane in a match delayed overnight. But fellow American, 16th seed Learner Tien is out, beaten by Hungarian veteran Marton Fucsovics.
