Metalloenzymes catalyze challenging chemical reactions. However, due to the unique reactivities of metals and their oxygen sensitive nature, characterization of metalloenzymes requires special skills. Consequently, many questions remain unanswered. In addition, due to the expansion of the genome sequence information, there remains many uncharacterized metalloenzymes that catalyze unprecedented reactions. We study the functions, mechanisms, and structures of metalloenzymes with the current foci on radical SAM enzymes and non-heme iron enzymes.