The Australian No.1 will also face American Taylor Fritz in the tournament's 'Jimmy Connors Group', with the top two advancing to the semi-finals in the end-of-season showpiece that begins on Sunday.
The other 'Bjorn Borg Group' will bring together world No.1 and defending champ Jannik Sinner, Alexander Zverev, Ben Shelton and one of either Felix Auger-Aliassime or Lorenzo Musetti.
Canadian Auger-Aliassime will nail down the eighth and final place, unless Musetti wins the title in Athens this week. On Thursday, the Italian reached the semi-finals with a 6-2 6-4 win over Alexandre Muller.
Whatever draw 'Demon' landed was guaranteed to be a fiendish test at a tournament featuring the world's top-eight players, but de Minaur has been talking bullishly about his chances in the Italian showpiece after losing all three of his round-robin matches on debut in 2024.
"I'm looking forward not just to make up the numbers this time and hopefully be able to do some damage over there," he had said after booking his spot in the recent Paris Masters.
The world No.7 de Minaur will probably consider being drawn with Alcaraz, against whom he's lost all his four encounters including the final in Rotterdam this year, the lesser of two evils, compared to having to play his nemesis Sinner, who owns a dispiriting 12-0 record against him.
There's also still a question mark over whether Djokovic, who beat de Minaur at Wimbledon this year, will even be at the start line in Turin for an 18th appearance at the season-ender.
Playing in Athens, the 24-time grand slam champ, who's playing his first tournament in over a month, said on Wednesday he wouldn't make a decision about Turin until after the Greek tournament was over.
But the 38-year-old certainly looked in the mood on Thursday as he beat Nuno Borges 7-6 (7-1) 6-4 to move into the semi-finals.
American world No.4 Fritz, who beat de Minaur in last year's round-robin stage at Turin's Inalpi Arena, shares a 5-5 career record with the Australian, though the pair have not met this year.
There's also concern around German world No.3 Zverev who lost his Paris Masters semi-final 6-0 6-1 against Sinner last Saturday while struggling with ankle problems.
Having been also beaten by the Italian in the previous week's Vienna Open final, Zverev must have given a sigh of dismay at learning he's drawn the world No.1 yet again.
While Djokovic and Musetti were still in Tour action on Thursday, de Minaur and Sinner were taking time out to train at the Inalpi Arena three days before the start of the tournament.
