
World Number Two Djokovic, playing his second match after an elbow injury, lost 6-2 3-6 7-5 to the Belgian in the quarter-final.
Goffin, ranked 13th in the world, progressed to the next stage after taking his fifth match point in a dramatic 11-minute final game.
The defeat has ended the Serb’s hopes for a third title in Monte Carlo, an ATP World Tour 1000 event which is considered a key part of preparations for the French Open in May.