Abstract: Porous graphene was prepared by hydrothermal method, and grapheme-polyanline (PANI) composites were synthesized in the dispersion system of porous graphene by in-situ polymerization using low-priced eco-friendly β-MnO₂ instead of the traditional polluting ammonium peroxydisulphate as chemical oxidant. The microstructures and electrochemical performance of the composites were characterized by X-Ray Diffraction Spectroscopy (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM), Cyclic Voltammetry (CV), galvanostatic charge-discharge measurements and electrochemical impedance measurements. Results show that the specific capacitances of the grapheme-PANI composite synthesized using β-MnO₂ as oxidant 350 F/g, and its capacitance retention is 67.7%, which has better electrochemical properties.