Alcaraz will be part of the Spain team, one of three confirmed by the International Tennis Federation on Tuesday, alongside Paula Badosa.
Hosts France will have Richard Gasquet and Alize Cornet, while Switzerland will feature Belinda Bencic and Leandro Riedi.
Three more nations are still to be confirmed for the event to be held at the Nice Lawn Tennis Club from July 19 to July 23.
Alcaraz's participation is a boost for the ITF as it re-launches an event that disappeared from the calendar in 2020 when it lost its spot ahead of the Australian Open as a result of the short-lived ATP Cup men's team competition.
"Alongside the Billie Jean King Cup and Davis Cup, the Hopman Cup is another ITF event that gives players the opportunity to represent their countries, and compete for something bigger than themselves," ITF President David Haggerty said at a news conference.
"After a brief hiatus since 2019, we are delighted to return this event to the tennis calendar."
The Nice Lawn Tennis Club will host the event up to 2027 as part of a five-year contract between the ITF and Barcelona-based company Tennium, which operates multiple ATP and WTA tournaments.
As in previous editions, teams will have one male and one female player, with ties featuring a men's singles match, a women's singles and a mixed doubles.
Six nations will compete in the 2023 and 2024 editions, with an expansion to eight nations from 2025.
The last edition of the competition, which began in 1989 and was named after Australian great Harry Hopman, saw Roger Federer lead Switzerland to the title against Germany.
The Hopman Cup has a rival in the United Cup mixed-gender team event, featuring 18 nations playing matches across three Australian cities, taking place before this year's Australian Open. The United States beat Italy in the final.
