There was never any danger of the world number one slipping to a stunning defeat, though, as he wrapped up a 6-3 6-2 victory in just an hour and 19 minutes.
Serb Djokovic, a 12-time Grand Slam champion, saved three set points at 5-2 down in the first, breaking back to level at 5-5 and taking the tie-break with his first set point. With neither player giving anything away in the decider, it was Thiem who tested Djokovic's fitness in the seventh game.
The 16-time Grand Slam champion is bidding for an 11th Monte Carlo title and a record 31st Masters title.
Thiem beat Djokovic in straight sets in the French Open quarterfinals previous year including 6-0 in the third but Djokovic won their other five meetings. Meanwhile, former world number one and Serbian tennis star Novak Djokovic will also look to seal quarter-final spot when he squares off with Dominic Thiem of Austria.
"It's [a] way better feeling if you go against him and know that you've beaten him already on this surface", Thiem said about his upcoming match against Nadal. Nadal has lost twice to him on clay, but produced a dominant display in the French Open semi-finals a year ago en route to his 10th Roland Garros title.
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"But it's the ultimate challenge for everybody, to play against him".
Khachanov could not stir up the same kind of resistance he produced in the first, Nadal losing only three points on serve in the second and securing an enticing encounter with Thiem with a forehand smash. "I'm pretty sure we're going to see him at the very top of the game pretty soon". "I think (it's an) awesome decision by him to take Marian Vajda back because it's the coach he won everything with nearly".
Japan's Kei Nishikori, another player making his way back from a long-term injury lay-off, defeated Italian Andrea Seppi 6-0, 2-6, 6-3. and will face Croatian world No 3 Marin Cilic in the quarter-finals.
Third seed Alexander Zverev needed three sets to beat fellow German Jan-Lennard Struff and he could face his brother in the next round if Mischa overcomes Richard Gasquet.
Goffin, semifinalist a year ago, next plays Grigor Dimitrov after the fourth-seeded Bulgarian beat Philipp Kohlschreiber 4-6 6-3 6-4.