In this study,an amine-coordinated cobalt phthalocyanine (CoPc)-based anodic catalyst was fabricated by a facile process,to enhance the performance of hydrogen peroxide fuel cells (HPFCs) and enzymatic biofuel cells (EBCs).For this purpose,polyethyleneimine (PEI) was added onto the reduced graphene oxide and CoPc composite (RGO/CoPc) to create abundant NH2 axial ligand groups,for anchoring the Co core within the CoPc.Owing to the PEI addition,the onset potential of the hydrogen peroxide oxidation reaction was shifted by 0.13 V in the negative direction (0.02 V) and the current density was improved by 1.92 times (1.297 mA cm-2),compared to those for RGO/CoPc (0.15 V and 0.676 mA cm-2,respectively),due to the formation of donor-acceptor dyads and the prevention of CoPc from leaching out.The biocatalyst using glucose oxidase (GOx) ([RGO/CoPc]/PE//GOx) showed a better onset potential and catalytic activity (0.15 V and 318.7 μA cm-2) than comparable structures,as well as significantly improved operational durability and long-term stability.This is also attributed to PEI,which created a favorable microenvironment for the enzyme.The maximum power densities (MPDs) and open-circuit voltages (OCVs) obtained for HPFCs and EBCs using the suggested catalyst were 105.2 ± 1.3 μW cm-2 (0.317 ± 0.003 V) and 25.4 ± 0.9 μW cm-2 (0.283 ± 0.007 V),respectively.This shows that the amine axial ligand effectively improves the performance of the actual driving HPFCs and EBCs.