A hydrophobic PbO2 electrode modified by surfactant OP-10 was prepared by electrodeposition. The electrode has good hydrophobic surface (the hydrophobic angle can reach 123°), high over point oxygen evolution (OEP) (1.60 V vs. SCE), and good service life (81 h). The electrode morphology and electrodeposition mechanism study found that the addition of OP-10 can help to build a dense PbO2 electrode surface, reduce the occurrence of side reactions, and promote the positive deposition of PbO2. As much as 30 mg L-1 of methylene blue, as the simulated pollutant, could be degraded in 80 min under conditions of 50 mA cm-2, initial pH = 7, and a concentration of supporting electrolyte of 0.15 mol L-1, which could be easily reached. Moreover, a practical dye wastewater was employed, proving the OP-10 modified PbO2 electrode is suitable for industrial applications, where the COD of dye wastewater can be reduced from 330 to 4 mg L-1 in 120 min.