In this paper, carbon paper (CP) was modified by three-dimensional reduced graphene oxide (3DrGO/CP) and binders. Based on physical (ﬁeld-emission scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy) and electrochemical tests (cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charging/discharging curves), the physical and chemical properties of 3GrGO/CP electrode were investigated. The physical characterization and electrochemical performance analysis indicated that the different binders significantly influenced the hydrophilicity and the wet surface area of electrode. Nitrogen doping three-dimensional reduced graphene oxide facilitates the electron transfer on electrode/electrolyte interface for both oxidation and reduction processes of 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (4-HO-TEMPO), provides more reaction area and reduces concentration polarization. Therefore, the modified carbon paper electrode exhibits better electrochemical activity and reversibility compared with the pristine carbon paper electrode in a methyl viologen (MV)/4-HO-TEMPO redox flow battery (RFB).