Herein, a Cu-hemin metal-organic-frameworks (MOFs)/chitosan (CS)-reduced graphene oxide (CS-rGO) nanocomposite with unique peroxidase-like bioactivity and good electrical conductivity was prepared for electrochemical H2O2 sensing for the first time. The prepared Cu-hemin MOFs/CS-rGO nano-composites were well characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray powder diffraction, UV-vis spectroscopy and electrochemical techniques. The results showed that after the Cu-hemin MOFs were formed on the CS-rGO surface, the crystalline structure of the Cu-hemin MOFs was kept while the size of Cu-hemin MOFs was decreased and the electrical conductivity of the nanocomposites was enhanced greatly as compared with that of Cu-hemin MOFs. The unique peroxidase-like bioactivity and good electrical conductivity as well as some novel properties of Cu-hemin MOFs/CS-rGO nanocomposites resulted in perfect electrochemical performances towards the reduction of hydrogen peroxide (H2O2), superior to some mimic enzymes. The Cu-hemin MOF/CS-rGO was used to construct a novel H2O2 electrochemical sensor which exhibited wide linear range (0.065-410 mu M) and low detection limit (0.019 mu M). The study might provide a new proposal for preparing perfect hemin-based materials as mimetic peroxidase in the electrochemical sensing. (C) 2016 Elsevier Ltd. All rights reserved.