A new cascade type cathodic catalyst containing hemin and glucose oxidase (GOx) is suggested for enhancing the performances of enzymatic biofuel cells (EBCs). In the cathodic catalyst, the upper GOx layer generates hydrogen peroxide (H2O2) by glucose oxidation reaction (GOR), and then actual cathodic current is determined by H2O2 reduction reaction (HRR) catalyzed by hemin, using the pre-produced H2O2. The reaction potential of hemin is positively shifted by the formation of coordinate bond between its core ions and amine groups, meaning that that of HRR deciding reduction onset potential of the catalyst is positively shifted. As materials providing the ligand containing amine groups, polyethyle- neimine (PEI) and imidazole propionic acid (IPA) are considered. According to evaluations, the reaction potential for HRR is favorably moved as the amounts of available ligand and coordinate bond increase. When IPA is applied, the reduction onset potential for HRR is shifted from 0.4 to 0.51 V and reduction reaction rate also increases from 55 to 86 mAcm-2. Based on that, the EBC using catalyst containing IPA shows superior performances, such as maximum power density of 66 mWcm-2 and open circuit voltage of 0.65 V.