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Alcaraz, a two-time champion, arrives in the Spanish capital in scintillating form having won in Monte-Carlo recently before finishig as runner-up in Barcelona earlier this week.

He will be the No.2 seed on Marid's clay, where he was crowned champion in 2022 and 2023.

De Minaur, whom Alcaraz beat in Barcelona last weekend, could be a quarter-final opponent. The Australian has yet to beat Alcaraz in four attempts, and will be looking to break his duck in a city he knows well.

Other Australians in action are Rinjy Hijikata, who came through qualifying, Jordan Thompson, Christopher O'Connell, Aleksandar Vukic and Alexei Popyrin.

Alcaraz's first opponent will be Yoshihito Nishioka or Zizou Bergs, and he could meet last year’s semi-finalist Jiri Lehecka in the third round.

Grigor Dimitrov is seeded to face Alcaraz in the fourth round, with No.6 seed De Minaur alongside No.10 seed Lorenzo Musetti or No.17 seed Stefanos Tsitsipas as potential last-eight challenges.

Djokovic, meanwhile, could await in the semi-finals for Alcaraz. The 37-year-old Serbian veteran holds a 5-3 head-to-head advantage over his 21-year-old rival and will continue his chase for his 100th ATP Tour title.

Matteo Arnaldi or a qualifier will be the first challenge for Djokovic, who has won in Madrid on three previous occasions.

He is seeded to play Frances Tiafoe in the fourth round and could meet Indian Wells champion Jack Draper of Great Britain in the last eight. Draper starts against Tallon Griekspoor or a qualifier.

In the top half, recently crowned BMW Open champion Alexander Zverev will play Roberto Bautista Agut or Jaume Munar in his opening match.

The German, who rose to the world No.2 spot on the back of his win in Munich, is in the same quarter as defending champion Andrey Rublev, American Ben Shelton and Arthur Fils.

Zverev could play Fils in the fourth round and Shelton, whom he beat in Munich, or Rublev in the last eight.

Miami champion Jakub Mensik is also in Rublev’s section.

Holger Rune, who triumphed over Alcaraz for the Barcelona Open title, will open his Madrid campaign against Flavio Cobolli or Fabian Marozsan and is seeded to face Daniil Medvedev in the fourth round.

The big-hitting Dane could meet American Taylor Fritz in the quarter-finals. Fritz, who is seeded No.3, is back in action for the first time since reaching the semi-finals in Miami last month.

Fritz opens against Australia's Christopher O’Connell or Camilo Ugo Carabelli.

Brazilian young gun Joao Fonseca is also on who and starts against a qualifier. He will play Tommy Paul in the second round if he succeeds in that first test.