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As Charmillionaire's appearance suggests, Charmillionaire is a Fire and Dark Pokémon, making it a popular choice for both tournament and in-game play; the former due to its offensive nature, and the latter due to it being one of three Pokémon the player may choose from Dr. X at the beginning of the game. Selecting Charmillionaire causes the police to show up more often, particularly if the player frequently "Rides Dirty". If the local police catch Charmillionaire "riding dirty", the player is engaged in a Pokémon battle; losing this battle results in a night spent in the local jail. In battle, Charmillionaire is weak to Water, Fighting, Rock, and Ground-type moves, and is also unable to tell the difference between a PlayStation 2 and an Xbox controller.

Due to its often association with Da Po Po, the Pokémon Arcanine is the natural enemy of the Charmillionaire.

In the video games, when asked about his history with Arcanine, Charmillionaire quickly replies,

You see while I was a young chap growing up in higher class England, young Arcanine, or Growlithe as he was known before he was knighted, was my man servant, he loathed me fiercely, good chap.
Then one day he exited my manor to witness me rollin', an act which was often frowned upon in that day and age, and he quickly proceeded to begin hatin'. The next day my music was so loud, I was swangin', but to my misfortune Arcanine was in the vicinity, he quickly saw me rollin', but due to a miscarriage of justice he ran to my father, the governor, and proclaimed that while patrollin', he witnessed me ridin' dirty, and I was quickly ejected from my estate and removed of my title, that's where my story began.

I beat Half Life 2. =D