Alcaraz won the French Open and Wimbledon this year to take his Grand Slam tally to four, before bagging the silver medal at the Paris Olympics.
The world number three from Spain, who also won the Indian Wells title, has qualified for the season finale for the third consecutive year and will be aiming to win the trophy for the first time after reaching the semi-finals last year.
An abdominal injury forced him out of the 2022 edition.
Sinner, last year's runner-up, qualified in August during his run to the Montreal quarter-finals, while 2018 and 2021 champion Zverev earned his spot after making the last eight of the US Open this month.
The ATP Finals, which features the world's best eight singles players and doubles teams determined by the separate Race To Turin rankings, will run from November 10-17.
