Nadal and Federer, who are back at the top of the sport's rankings after sweeping the four Grand Slam titles in 2017, are expected to be selected by Europe team skipper Bjorn Borg to play doubles as well as singles.
It will the two legends' first appearance on the same side of the court in a rivalry which has spanned the best part of two decades.
Joining Federer and Nadal in the Europe team are fellow top 10 players Marin Cilic, Alexander Zverev, Dominic Thiem with former number four Tomas Berdych making up the squad.
Team World, skippered by John McEnroe, features four Americans -- Frances Tiafoe, Sam Querrey, John Isner and Jack Sock as well as Australian crowd puller Nick Kyrgios and Canadian teenager Denis Shapovalov.
There are four matches a day -- three singles and a doubles. Nadal, who added the US Open to his Roland Garros title earlier this month, said he may be a little ring-rusty over the weekend having taken a break following his New York triumph.
"I didn't practice here yet, of course after the US Open. After a big event you go down a little bit, you need to recover energy. I have today and tomorrow to practise hard and let's see then," said the Spaniard.
Last weekend, the semi-finals and play-offs for this year's Davis Cup took place but without the likes of Federer who opted out of Switzerland's tie against Belarus.
The Davis Cup schedule has come in for a constant stream of criticism from top players wary of adding more pressure to their calendars.
However, Kyrgios did play at the weekend as Australia lost to Belgium in the semi-finals in Brussels. He said he was looking forward to the different nature of the Laver Cup.
"We're definitely underdogs, going into it, but I think we've got the weapons and we can definitely win this competition. I love the team event, I love to get behind my teammates and do everything I can as a competitor or as a team player to get the win.
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