Del Potro, the youngest player in the field and a tournament debutant, gave everything he had in his final group match but the rising Argentine star could not match Davydenko's experience.
World No 5 Davydenko will now make his second appearance in the semifinals in four attempts at the $4.45 million season finale. He also advanced from the group stage in 2005 before crashing out to another Argentine, eventual winner David Nalbandian.
"I am happy to be in the semifinals because this was my last chance to qualify," the Russian told reporters after the match.
Del Potro rarely looked comfortable during the match as he struggled to keep up with Davydenko's pace. He hung on for a while, however, closing the gap in the first set from 4-1 to 4-3 before suffering a collapse.
In the first match of the day, world No 3 Novak Djokovic of Serbia hit a wall against Frenchman Jo-Wilfried Tsonga, who rallied from one-set down to clinch it 1-6, 7-5, 6-1.
Although Djokovic had already qualified for the semifinals with his previous victories over Del Potro and Davydenko, the 21-year-old was praying for a win to catapult him past Federer in the world rankings and finish the year as world No 2, a turnaround that depended on him not conceding a game and Federer losing to Briton Andy Murray in today's crucial decider.
"The important thing is that I'm through. I achieved everything I wanted in this tournament. Well, it is still not the end. I think I have enough quality to go further," the Serbian said.
Djokovic still tops his group despite the defeat, followed by Davydenko. With Andy Murray already going through from the other group, defending champion Federer and Frenchman Gilles Simon will battle for the last berth today.
If Federer, who plays second, beats Murray then Simon's match against Czech alternate Radek Stepanek will have no bearing on the Swiss star's progression as he will automatically advance. If Federer loses, he is out, making these the first semifinals in seven years not to be graced by his presence.
Federer, who is nursing a back injury and an unspecified stomach complaint, is gunning for his fifth title at the tournament.
"It's good for the sport to see young guys coming up and doing well," said Djokovic. "Roger is still one of the best players in the world even though he was not (in the best) shape this year.
"It's a big challenge for him to come back from the first part of the year, but now the range of players who are candidates for the (world's) top spots is bigger."
If Federer beats Murray in straight sets today he will top the group and meet Davydenko in the final four. A three-set win would place him second and therefore in line for a court date with Djokovic.
Davydenko said he would prefer to play Murray rather than the former world No 1, who holds a stunning 12-0 record against him.
"Although he is not playing his best tennis at the moment, he is always a different person when I play him," the Russian said.
"I think I will have more chances (against) Murray."
Davydenko is likely to finish within the world top 5 for the fourth consecutive year but he is not happy with his sub-par performances at big tournaments. He has failed to make the last eight at a Grand Slam since 2004.
"I need a new result, a better result. I have already been in the finals (at the Masters Cup). I want to be in the final this time."
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