Yes, this is supposed to be Luigi.

Luigi Mario, also called Luigi Mario Luigi to distinguish him from the original Luigi, is the form of Luigi who appeared in the live-action Super Mario Bros. movie. Similar to the "real" Luigi, he is a plumber and the younger brother of Mario Mario Mario. Some people consider him the worst-looking form of Luigi in existence, and with his competition, that's saying a lot. His lack of a moustache has much to do with this, but also helped him evade form hunters during the Form Wars.

"Aren't you a mite puny to go up against Ganon?"
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