At the draw in Paris, Djokovic, seeded third, was pulled out in the same half as the US Open champion from Spain, meaning they could meet in a blockbuster last-four showdown.
Alcaraz won their only other previous meeting, in Madrid last year. Two-time winner Djokovic, looking for a 23rd grand slam title, faces American Aleksandar Kovacevic in the first round.
Alcaraz, 20, and second seed Daniil Medvedev will begin their campaigns against qualifiers.
💥 Potential quarter-final clashes in the men’s draw 💥
Alcaraz vs. Tsitsipas
Djokovic vs. Rublev
Rune vs. Ruud
Sinner vs. Medvedev#RolandGarros
— Roland-Garros (@rolandgarros) May 25, 2023
British number one Cameron Norrie takes on unpredictable Frenchman Benoit Paire, and he could run into Alcaraz in the fourth round.
Dan Evans faces a tough opener against Australia’s Thanasi Kokkinakis and Jack Draper meets Tomas Martin Etcheverry of Argentina.
They are the only three British players in the main draw at Roland Garros after Kyle Edmund, who has been beset by knee problems for the past two years, withdrew due to a wrist injury.
Andy Murray and Emma Raducanu pulled out earlier this month, while six British women lost in the qualifying rounds.
In the women’s draw, 2022 champion Iga Swiatek will begin her title defence against Spanish world number 67 Cristina Bucsa.
— LTA (@the_LTA) May 25, 2023
The world number one could face Wimbledon champion Elena Rybakina, seeded fourth, in the semi-finals.
Second seed and Aryna Sabalenka will face Ukrainian Marta Kostyuk in the opening round.
Last year’s runner-up Coco Gauff starts against former French Open junior champion Rebeka Masarova of Spain.
Third seed Jessica Pegula and last year’s Australian Open finalist Danielle Collins meet in an all-American clash, and two-time grand slam winner Victoria Azarenka takes on 2019 US Open champion Bianca Andreescu.