A highly hydrophilic ordered mesoporous carbon-poly(vinyl alcohol) composite with large surface area and good biocompatibility, and exhibiting efficient immobilization and biosensing of protein [e.g., hemoglobin (Hb)] was prepared by intermittent microwave heating techlnique. The as-prepared composite with immobilized Hb is tested for direct electrochemistry and biosensing. The immobilized Hb at the modified electrode had a high adsorption with 32 wt% of the proteins. Moreover, the modified electrode retained its native structure, with improved interfacial electron-communication rate, and showed a good electrochemical performance to detect H2O2, as verified by Raman, UV-Vis absorption, and electrochemical impedance spectroscopies, as well as steady-state current measurements. The proposed biosensor shows a sensitivity of 9.8 mu A mM(-1) and responds in less than 5 s when the protein concentration ranges from 87.5 to 0.4 mu M. This work provides an efficient strategy and a new promising platform for both fundamental investigation of the redox reactions mechanism and the development of third-generation biosensors.