The reigning world No1 delivered an emphatic statement with a dominant victory over rival Carlos Alcaraz in Saturday night's high-profile second semi-final tie in Turin, brushing aside the Spaniard in straight sets 6-3, 6-2 to take a 3-2 lead in the head to head.
Jannik Sinner now stands in the way of Djokovic and a seventh triumph in the annual season-ending tournament that would take him clear of great rival Roger Federer for the all-time lead.
Sinner became the first Italian player ever to reach the showpiece match earlier on Saturday, beating 2020 champion Daniil Medvedev with a dominant display in a one-sided third-set decider to prevail 6-3, 6-7, 6-1 in front of a celebratory home crowd.
Sinner and Djokovic have met four times in the past, with Djokovic beating him in both the semi-finals and quarter-finals at Wimbledon in recent years, plus at the 2021 Monte Carlo Masters.
However, world No4 Sinner did emerge victorious from their last meeting in the group stages of these finals, winning a hard-fought contest 7-5, 6-7, 7-6 on Tuesday.