Djokovic lost his opener to Alejandro Tabilo, having been the third seed at the ATP Masters 1000 event earlier this month.
He fell to the Chilean 6-3, 6-4, with the 24-time Grand Slam champion now continuing his search for a 100th ATP title elsewhere.
Nadal meanwhile won the tournament a stunning 11 times, more than any other player, which includes an Open Era record eight successive wins.

Novak Djokovic proud of 2013 Monte Carlo Masters final win over Rafael Nadal
The Serbian has now discussed the Spaniard’s record at the event, having been asked on BB Tennis about ending Nadal’s phenomenal winning streak
“We haven’t talked about that but I remember my first win against him in Monte Carlo,” said Djokovic. “It was in the final of 2013.
“I played one of my best matches on clay and it came at the right moment because you know it took me years to try to figure out this puzzle and formula for beating Nadal on clay.
“So not many players have succeeded in several years and multiple times playing at different tournaments and I can proudly say that I have managed to do it at the biggest tournaments, including Roland Garros. Nadal on clay was a big mountain to climb.”
Novak Djokovic among Rafael Nadal’s victims in stunning Monte Carlo Masters record
Nadal claimed many victims during his fantastic dominance at the Monte Carlo Masters, which included Djokovic on two occasions.
But after losing the 2009 and 2012 finals to his nemesis, the Serbian emerged victorious 6–2, 7–6(7–1) in 2013.
Djokovic would win the tournament once more in 2015, but even then Nadal was able to recover and win three successive Monte Carlo Masters titles.
The legendary figure was simply unstoppable on clay for much of his career, epitomised by his record 14 French Open titles.