The final match of Roger's illustrious career will be in the doubles at the London event.
The 20-time Grand Slam winner said last week that he would retire from the sport.
He can't play singles due to a knee problem.
"It's an event I don't want to mess with, but I know my limitations," said the 41-year-old Swiss, who hopes to pair up with the Spaniard.
The first alternate for the team tournament will be Matteo Berrettini.
In last year's Wimbledon quarter-finals, he was beaten by Hurkacz.
The six players from Europe and the world team are usually required to play at least one singles match during the three-day event.
"I asked Bjorn if I could play one doubles on Friday, then Matteo came in," he said.
I haven't played in awhile.
There is a chance of a link-up with Nadal.
He said that playing doubles with Nadal would be the most beautiful thing.
"I want to play at a level that is ok for me but also for the fans and the event, also enjoy myself, but at the same time I want to try my best and to soak it all in," he said.
It's going to be very different over the next 72 hours, but I want to look forward to it, I signed up for it and I wanted to be around.
I wanted to be around and I didn't want to be a ghost.
I feel like I'm at a party at the Laver Cup.
Team Europe will face a world team of Felix Auger-Aliassime, Diego Schwartzman, Alex de Minaur, and Jack Sock.
In the evening there are two singles matches and a doubles match.
It made sense for him to retire in London because it had been the most special place in his career.
"You don't need a lot of records to be happy, I can tell you that," the eight-time Wimbledon champion said.
The Swiss said he decided to retire after stopping believing he could continue playing.
He said that he had been on thin ice since he played Wimbledon.
There was a limit to what I could do, so I tried to return.