Del Potro was to be replaced by Jose Acasuso in the best-of-five series, which Spain lead 2-1. Acasuso will face Fernando Verdasco, who replaced David Ferrer.
Argentina's top-ranked player at No. 9, del Potro injured his right thigh in a four-set loss to Feliciano Lopez on Friday. He was not able to recover in time for Sunday's match despite undergoing intense treatment throughout the day Saturday.
"We didn't want to risk starting the match and then, after two or three games, have to retire because of the injury," Del Potro said. "It would have been much worse if that happened."
The 48th-ranked Acasuso will be playing his first match in this year's Davis Cup final. He has a 5-2 singles record in the competition, and leads Verdasco 1-0 overall. The 20-year-old Del Potro, one of the hottest players on tour this year, was 4-2 in Davis Cup singles.
"I would like to be playing, but Acasuso is in a better position now," Del Potro said. "I'm sure he will do his best and we will all be supporting him."
The 16th-ranked Verdasco, 3-3 in Davis Cup singles, replaced Ferrer after helping lead Spain to a key win in the doubles on Saturday, playing with Lopez. The 12th-ranked Ferrer lost his singles match to David Nalbandian on Friday.
Nalbandian will face Lopez in the final match of the day.
Argentina needs to win both matches at Islas Malvinas Stadium to clinch its first Davis Cup final. Spain, without top-ranked Rafael Nadal, is one win away from its third triumph.
Feliciano Lopez and Fernando Verdasco put Spain one victory away from winning the title when they beat David Nalbandian and Agustin Calleri 5-7 7-5 7-6 6-3 in the doubles in Mar del Plata.
Spain, champions in 2000 and 2004 and runners-up on three other occasions, came into the final unfancied following the withdrawal of world number one Rafael Nadal through injury.
But Lopez, having stunned number one Argentine Juan Martin del Potro 4-6 7-6 7-6 6-3 in the second singles after Nalbandian had thrashed David Ferrer in straight sets in the opening rubber, once again shone as the visitors overcame an inauspicious start to tough out what may prove to be the decisive encounter.
Both of the two opening sets were as tight as the scoreline suggested, with the hosts getting their noses in front after Vardasco double faulted in the 11th game. Nalbandian then closed out the set after first staving off a triple break point.
But the Spaniards came roaring back and pinched the second set by the same margin, aided by Calleri fluffing a smash and then a backhand volley long to give the visitors the decisive break in the 12th game.
In the third set, it looked as if the Spanish tandem would rue letting slide a 5-1 lead. Verdasco strode up to serve out and a Nalbandian return into the net brought up a first set point.
But Verdasco produced a double fault as the hosts closed the gap in the seventh game and Lopez then dropped serve in turn, midjudging a volley on a ball which was going out in any case as the Argentines forced their way back to 4-5.
That sparked such emotion among the 10,000 home fans that it brought a warning from the umpire of a potential penalty unless they calmed down. A Calleri hold made it 5-5 and two further games went with serve to force the tiebreak.
This time it was Argentina who threw away the early initiative gained as they streaked 5-1 clear only for Nalbandian to miss a volley before Verdasco produced a clean winner and then Calleri netted a forehand to gift the Spanish a 2-1 lead.
With Nalbandian tiring visibly by the point, the Spanish snatched a break in the fifth game and then also broke Calleri in swift succession to move out to 5-2.
With the Argentines wilting, Verdasco produced a brutal serve to finish them off in over three hours to send the 400 flag-waving Spanish fans delirious.
"This was an important victory, it gives us life," said Spain captain Emilio Sanchez Vicario. "We need one more game.
"The third set was full of different emotions," Sanchez Vicario said. "It was an incredible finish and gave us confidence to keep going."
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