Swiss ace Federer will partner fellow all-timer Nadal in the doubles, the man from Basle bringing an end to an illustrious career in the company of his greatest rival.
The prospect of being a team-mate on court with Federer in London is something that will be "unforgettable" for Nadal.
"After all the amazing things that we shared together on and off the court, to be part of this historic moment, it's going to be something amazing and unforgettable for me," Nadal said in Thursday's press conference.
"I hope I can have a good time playing at a decent level and hopefully together we can create a good moment and maybe win a match.
"But I hope that the crowd will be supporting a lot. I'm super excited to be here with the team and of course to be on the court and having Roger next to me one more time will be something that I am very looking forward to.
"We were able to create an amazing rivalry together, and on the other hand, something that we are probably very proud [to have had], I have been a friendly rival which is not easy sometimes because we are playing for such important things for our tennis careers.
"But at the same time, we were able to understand that in the end personal relationships are more important than sometimes professional things, and we were able to handle it I think the proper way.
"Tomorrow it's going to be a special thing. I think it will be difficult to handle everything, especially for Roger, without a doubt, but for me too. One of the most important players, if not the most important player, in my tennis career is leaving and to leave at this moment will be difficult."
Federer is also looking forward to the match and partnering with Nadal, though he concedes it will be a difficult test as the Team Europe pair tackle Team World's Frances Tiafoe and Jack Sock.
"Of course, it's super special playing with Rafa," Federer said.
"It feels really different. Also just walking out on the court and having the chance to play with the likes of Rafa or Novak also in the past has been an amazing experience for me.
"So, to be able to do that one more time, I'm sure it's going to be wonderful. I'll try my very best and I hope to be good out there. And of course, I'll enjoy it but it will be hard."