The Serbian ended victorious on the centre court, claiming a 2-6 6-1 6-4 win over Alexandr Dolgopolov.
The world number one experienced a tough start to the first set of the third round after Dolgopolov stole the break and managed to hold on to his serve to take a 4-2 lead in the opening stages.
The Ukrainian continued his dominance and Djokovic, who learned of the death of his grandfather just hours before the clash with the 21-year-old, failed to stamp his authority on the contest and relinquished a one-set lead in Monaco.
Despite an unsettling start to the third-round contest, Djokovic managed to find his form and stun his opponent by cruising to a 6-1 second-set win.
A change in the weather forced the players off the court in the third game of the deciding set, but once the rain had stopped the opponents continued to hold their serve, creating a tight finish to the match.
Djokovic was the first to take the break and the advantage in the third and final set, which provided him with the chance to launch to victory.