Yes there is a reason. Mario as Ты know is the short, brave, older, heroic brother and Luigi is the tall, younger, cowardly, shy brother. They would be considered polar opposites. If u have a color wheel или have studied it in Art или sumthin, then Ты would know that red is straight across from green therefore red and green are opposite colors. Though i like Luigi better...
I might of thought because since they're Italian, green, red and white are the Цвета of the flag of Italy. Mario red, Luigi green and when both of them use the цветок to shoot огонь balls they're white. plus they have Italian names too.
Mario is red because it contrasts the background nicely. Luigi is green because green is opposite of red, and still has a good contrast against the background.