Nadal, who returned to action after a months-long layoff at last week's Barcelona Open, has struggled with injuries for the last two years and has said he expects to retire after the 2024 season.
This will be the 22-time Grand Slam champion's fourth appearance at the three-day team tournament, which pits six top men's players from Europe against six of their counterparts from the rest of the world.
Nadal last played at the Laver Cup in 2022, when he teamed up with his rival Roger Federer, which was the Swiss great's last match.
"I have some really special memories from my Laver Cup experiences, including all the emotions from London two years ago playing alongside Roger for the last time," Nadal said in a statement.
"At this stage in my career, I really want to go out there and make the most of every opportunity I am given.
"Teaming up is always an incredible experience and I have always enjoyed it, the competition is different and exciting. I'm looking forward to going to Berlin and helping Team Europe win back the Laver Cup."
Top-10 players Carlos Alcaraz, Daniil Medvedev and Alexander Zverev are among the other players that will be part of Team Europe in this year's competition, which will be held in Berlin from September 20th to 22nd.
"Rafa is an absolute legend in our sport, a true champion in every sense of the word," Team Europe captain Bjorn Borg said.
"It's my last year as captain. Having him on Team Europe this year was a goal of mine and I'm thrilled he has accepted my invitation and will be with us in Berlin."
