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This paper investigates the relationship between structure and electrochemical performance of reduced graphene oxide (RGO) prepared via heat treatment and chemical reduction method. Structure and morphology of RGO was characterized by means of Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction and Brunauer-Emmett-Teller. Electrochemical performance of RGO electrode supercapacitor was investigated in the organic electrolyte by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance. The results show heat treatment RGO has high graphitization degree, less surface oxygen-containing groups, good charge-discharge efficiency and stable life cycle. The chemical reduced RGO has single-graphene structure, high specific surface area, high specific capacitance and low internal resistance. The ascorbic acid reduction RGO exhibits good comprehensive electrochemical performance: Its specific capacitance was 220.7Fg-1, internal resistance was 3.0Ω and charge-discharge efficiency was 97.0% after 2000cycles of charging/discharging tests.