Djokovic was the first of the two to advance to the final on Friday, winning five of the last six games from 3-1 down in the second set to defeat German qualifier Yannick Hanfmann, 6-3, 6-4.
Despite the early trouble in the second set, it was a much less complicated result for Djokovic than the pair's last meeting, a 4-6, 7-5, 6-3 victory for the Serb in Shanghai a few weeks ago.
The 24-time Grand Slam champion is now one win away from the 101st tour-level title of his career. He's already one of just three men in the Open Era to surpass 100 career titles, alongside fellow legends Jimmy Connors (109) and Roger Federer (103).
Musetti followed Djokovic into the final later in the day after a dramatic 6-0, 5-7, 7-5 victory over Sebastian Korda, in which he originally led by a set and a break, 6-0, 4-3, before the American clawed back and even held a match point with Musetti serving at 4-5 in the third set, before the Italian regrouped to sneak it out.
The Italian is seeking the third ATP title of his career this week, having won his first two in 2022, in Hamburg and Naples.
But more importantly, he's now a win away from becoming the eighth and final qualifier for the ATP Finals in Turin. He's currently No. 9 in the Race to the ATP Finals standings, and would pass Felix Auger-Aliassime for the No. 8 spot by winning the title in Athens.
"I'm not really lucky with the finals these past years—three years I've been losing finals. But hopefully the story will change starting from tomorrow," said Musetti, who's lost his last five finals.
"I will of course play for two goals—one, of course, is the title here, and the other one you probably know. I'm really, really looking forward to playing this match tomorrow against a legend."