In this work, Sodium p-styrene sulfonate (SSS)/PbO2 electrode was successfully prepared and further applied for the electrocatalytic degradation of methyl blue (MB). 95.8 % of methylene blue degradation via PbO2 electrodes was observed at the optimized conditions (100 mg/L-1 of MB solution, current density of 30 mA·cm−2, pH=5, 180 min). When compared with PbO2 electrodes, SSS/PbO2 electrode was found to possess most effective electrocatalytic activity due to its higher oxygen evolution potential, lower charge transfer resistance, and longer service lifetime. When the concentration of SSS increases to 2vt%, the grain size of PbO2 decreases from 21.79 nm to 19.42 nm, and the degradation rate of MB was enhanced for 5 %. Besides, the degradation rate of SSS/PbO2 electrode remained 86 % after 10 cycles, indicating that the stability and catalytic activity of the electrode were improved when the PbO2 was decorated by SSS. Moreover, the law of degradation of MB catalyzed by SSS/PbO2 electrode follows the first order kinetics. Furthermore, the energy consumption and mineralization efficiency of the SSS/PbO2 electrode were 68.73 kWh· L-1 and 4.39 %, respectively. Finally, a possible mechanism was proposed, which was further uncovered by DFT calculations.