The 10th edition of the tournament will take place at the Intuit Dome in Los Angeles from September 24th to 26th.
Team World is made up of players from outside Europe. The annual tournament, launched in 2017, is intended to be tennis's equivalent of golf's Ryder Cup.
World number one Zverev will make a record eighth Laver Cup appearance in Los Angeles, having been part of Team Europe's six title-winning campaigns since making his debut at the inaugural event in Prague in 2017.
The German delivered the decisive points in this year's 13-5 victory over Team World in London and also sealed triumphs in Chicago in 2018, Geneva in 2019 and Boston in 2021, when he teamed up with Andrey Rublev in the doubles.
"I've been part of Laver Cup since the very beginning and it's become one of my favourite weeks of the year," Zverev said in a statement.
Alcaraz will make his fourth consecutive appearance after debuting in Berlin in 2024, where he beat Taylor Fritz to secure the title.
"I’m really happy to be coming back for my fourth Laver Cup and to be playing alongside Sascha again,” Alcaraz added.