Djokovic won both of his opening round-robin matches and booked his place in the semi-finals with a game to spare.
The world No 1, who has won four of his last six events, will be looking to go through as the group winner when he takes on Marin Cilic tomorrow night.
Meanwhile in Group Lleyton Hewitt, Anderson and Roger Federer will fight for the top spot in tonight’s evening session.
But Austrian Thiem reckons Anderson will come out on top because of the court at London’s O2 Arena.
“[Djokovic’s] the top favourite, that’s for sure,” Thiem said.
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“But Kevin was impressive against me and also against Kei [Nishikori].
“If he’s serving well, I think even Novak has troubles. He beat him also at Laver Cup.
“I think the conditions here are great for him. He’s feeling well from the baseline, hitting a lot of winners, not doing many unforced errors.
“So I think right now Kevin would be the biggest challenge for Novak.
“I would not be that surprised if we see these two guys in the finals.”
Thiem can still progress out of the group stages but he needs Federer to win fewer than five games against Anderson.
But the world No 8 is not confident of that happening and he has already begun thinking about next season.
“Now I will go on a one week holiday, then I spend a few days at home,” he added.
“I think the most important period of the season is starting, the off-season, the only time where we have time to practice and to really improve all the stuff what we need to work for. That’s how it is in tennis.
“I think we cannot complain about it because we have a very nice life with that.
“The only thing which would be better if the year would have 13 months.”