All money raised from the match will be split between two military charities, Rugby For Heroes and Hull 4 Heroes.
Rugby Union All-stars are representing the south and Rugby League All-Stars representing the north, where the code is more traditionally played.
England World Cup winner and former Gloucester player Mike Tindall is the Union All-Stars captain.
"The tough thing is that in Rugby Union you're taught to bounce back onto your feet fast, whereas in Rugby League you've got to lie on them for as long as possible to slow the speed of the ball down," Tindall explained.
"It's always a challenge but it's about being able to adapt."
Wearing the armband for League All-Stars is former Great Britain Rugby League international Keith Senior.
"[There is a] Union-League rivalry but the core skills are exactly the same," Senior said.
"But watching the two play the opposite core is like watching 7-year-olds on a rugby pitch!"