Less than two weeks after Djokovic beat Nadal to claim the ATP World Tour Finals title in London, the pair met again in Santiago as part of local hero Nicolas Massu's tennis farewell.
The former Olympic champion announced his retirement earlier in the season.
Now 34, Massu kicked off the night with a 6-4 6-2 victory over David Nalbandian before Djokovic and Nadal took to the court.
And again it was the current number two who prevailed, winning 7-6 (7/3) 6-4.
Both Djokovic and Nadal continue their end-of-season South American tour in the coming days.
Nadal meets Nalbandian, who is also retiring, in Cordoba on Thursday night before facing the Argentine again in Buenos Aires on Saturday.
Djokovic and Nadal then clash for a second time in the Argenine captial on Sunday.