The star-studded 2022 edition will take place in London in September with Federer, Nadal and Murray previously having committed to the event.
But now, this year's Wimbledon champion has thrown his name into the mix to complete the 'Big Four' who share a staggering 66 Grand Slams between them.
"I'm really excited to be joining Team Europe again for the Laver Cup in September," Djokovic told reporters after his triumph at Wimbledon earlier this month.
"The Laver Cup is the only competition where you can have all the big rivals, the 'Big Three', 'Big Four' players joining in the same team,".
"Of course, it's a very different and exciting concept for us players, but also for the fans around the world."
The 21-time Grand Slam winner is set to make his second Laver Cup appearance after being a part of Europe's winning side in 2018 where he teamed with Federer in the doubles, eventually losing to Team World's Kevin Anderson and Jack Sock.
The Laver Cup is an annual tournament formed in 2017 and is intended to be the 'Ryder Cup' of tennis with Europe's top talents facing off against a team comprised of players from the rest of the world.
The 2022 tournament will take place at the O2 Arena from 23-25 September.
Bjorn Borg will lead a rampant Team Europe in London after having lifted the trophy at all four previous editions of the Laver Cup.
Meanwhile, John McEnroe will captain team World and will have Felix Auger-Aliassime, Taylor Fritz and Diego Schwartzman at his disposal for the event.
Djokovic could have plenty of preparation time as he is set to miss the US Open next month.
America requires non-citizens to be vaccinated against Covid-19 to enter.