The hydrophobic polyvinylidene fluoride (PVDF) was doped in PbO2 anode through coelectrodeposition method. The morphology, structure, and contact angle of the electrode were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), and contact angle goniometer. Electrochemical properties were determined by linear sweep voltammetry (LSV) and accelerated life test. Experimental results showed that PVDF-doped PbO2 still possessed beta-PbO2 crystallographic structures. Contact angle, oxygen evolution potential, and life span increased with PVDF doped amount. The oxygen evolution potential of Ti/SnO2-Sb2O5/PbO2-PVDF (1 wt%) was 1.83 V (vs. saturated calomel electrode, SCE). Results of the accelerated life tests of different anodes illustrated that 45.75 h for Ti/SnO2-Sb2O5/PbO2-PVDF (1 wt%) was much longer than the 8.37 h for Ti/SnO2-Sb2O5/PbO2 and 2.45 h for Ti/PbO2. Approximately 92.1% of perfluorooctanoic acid (PFOA) degradation was achieved in 180 min at initial pH 3 at applied current density of 40 mA/cm(2) at Ti/SnO2-Sb2O5/PbO2-PVDF (1.0 wt%).