Scholes will be playing alongside England captain Jill Scott, Jermain Defoe and Danny Dyer while Nani will be in action for the World XI with skipper Usain Bolt, Patrice Evra and Lee Mack.
But Nani will be coming into the match in impressive condition, boasting bulging biceps and abs that would leave Cristiano Ronaldo in awe.
And Scholes is not looking forward to reuniting with the Portuguese winger, who he played with at United for six years.
Posting a picture of his own physique on Saturday, Scholes wrote on Instagram: "Looking forward to playing against Nani tomorrow (am I f***).
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"Another two weeks and I'd have been like Nani and Patrice Evra (would I f***)."
And he even tagged Gary Neville in the post, who will also be playing for England.
"Hope my mate Gary Neville is ready for them," before Neville hit back: "No beer tonight please."
Evra was among those to reply, saying: "Gary Neville, Scholesy, we cannot wait to see you tomorrow.
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"Old Trafford, home sweet home. No beers tonight, no fish and chips, we love you guys."
Nani also soon got in contact, referring to Scholes' somewhat problematic defending skills, saying: "Be careful with your tackles tomorrow."
The 36-year-old has only just recovered from a partial tear of the anterior cruciate ligament that saw his time at Melbourne City cut short.
He suffered the injury in January and has made a miraculous recovery, but it was not enough for the Australian side to keep him for a second year.
Nevertheless, Nani has not allowed his serious injury to hamper his efforts in the gym and he looks bulkier than ever.
United fans might be surprised to see their old player looking absolutely shredded, considering he was seen as somewhat lightweight during his stint at Old Trafford.
Despite being without a club, Nani combines a range of sprint drills with strength work as he eyes another year in professional football.
The former Red Devils star has travelled the world since leaving United in 2015, playing for Fenerbahce, Valencia, Lazio, Sporting Lisbon and MLS outfit Orlando City.