"He has one of the biggest serves in the sport," Djokovic said. "He has one of the most aggressive forehands. I just needed to stay tough."
Djokovic, undefeated in last year's Finals, improved to 2-0 in Group B after defeating Roger Federer.
Federer made light work of Richard Gasquet to clinch his first round-robin win, defeating the Frenchman 6-4, 6-3 to boost his chances of making the semifinals for an 11th time.
Nadal qualified from Group A on Wednesday when he beat Stanislas Wawrinka to clinch the season-ending No. 1 ranking for the third time in his career.
Djokovic and del Potro couldn't reproduce their epic Wimbledon semifinal but still exchanged brutal groundstrokes early on, with Djokovic winning the long rallies.
Playing more accurately and trying to shorten the points, del Potro soldiered on in the second set and was rewarded for his patience as he converted his first break point of the set in the sixth game thanks to a lucky net cord. The former U.S. Open winner then forced a third set.
In the third game, del Potro had 15-40 after Djokovic's first double fault of the match. The Serb saved the first break point with an ace and del Potro wasted the other with a botched forehand. The episode sapped del Potro's morale and he lost his serve at love in the sixth game. It was decisive.
In a match pitting together two stylists, Federer and Gasquet were ordinary. Federer quickly took control and broke Gasquet four times. The Frenchman hit only 11 winners and looked inhibited throughout.
Federer, who has won a record six year-end championships, was not having a great day either he had 30 unforced errors but prevailed on important points as Gasquet converted only one of his six break chances. Federer needed five match points to earn his 43rd Finals win.
"It is a big win for me," said Federer, chasing only his second title of the year. "I'm coming back from a lot of sort of ups and downs, resetting things, trying out things, making sure I get my confidence back, my movement and so forth."
Only once in his previous 11 Finals has Federer failed to advance to the last four. A win against del Potro on Saturday will guarantee him a spot in the semis, while Gasquet became the second player to be eliminated, following David Ferrer.
Federer has only three victories against top-10 opponents in 2013, including one against del Potro in Paris last week.
"I think that win for me in Paris psychologically was very important," Federer said. "I could beat top-10 guys, I beat Richard, I beat Juan Martin last week. I truly believe my confidence is higher, and that's what I need to beat the best, and Juan Martin is part of that group honestly."
- AP