The draw for the tournament that begins on Sunday served up the appetising prospect of a tussle between the reigning French Open champion and a player many expect to enjoy huge Roland Garros success.
Alcaraz, 18, last week became the youngest men's champion at the Miami Open, and he has soared to No.11 in the ATP rankings after sitting outside the top 100 this time 12 months ago.
He won an ATP 250 tournament on clay last year in Umag, and an ATP 500 on the surface in Rio de Janeiro in February, but earning a Masters 1000 hard court title in Miami highlighted the scale of Alcaraz's rapid improvement.
Both he and Djokovic will receive a first-round bye in Monte Carlo and must then win twice to set up a meeting at the last-eight stage.
Alcaraz may have to beat the in-form Indian Wells champion Taylor Fritz in the third round, with Marin Cilic and Sebastian Korda also potential early opponents for the young Spaniard.
Djokovic will not be taking a quarter-final place for granted, either. If he navigates his opening match, the Serbian could face a dicey third-round clash with Spain's Roberto Bautista Agut or the player to whom he lost at the Round of 16 stage last year, Britain's Dan Evans.
Rafael Nadal is absent after suffering a stress fracture of a rib during his Indian Wells final defeat to Fritz.