Coal gasification wastewater (CGW) contains a large amount of toxic pollutants, which seriously affects the subsequent biochemical treatment. In order to investigate the efficiency of electrocatalytic oxidation on pretreatment of CGW, lead dioxide electrodes doped with PEG and Bi were successfully prepared. Scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction were comprehensively used to characterize the lead dioxide electrode and the electrochemical performance was also tested by linear sweep voltammetry curve, cyclic voltammetry curve and AC impedance. Biodegradability and toxicity of CGW were evaluated by dehydrogenase activity and acute toxicity, respectively. Results showed that the doping of PEG and Bi significantly improved the electrochemical performance and catalytic oxidation performance of lead dioxide electrodes. The degradation rate of phenol by Sn-Sb/PbO (PEG + Bi) electrode were 1.57 times of that by pure lead dioxide electrode. The removal of TOC and total phenols were 53.2% and 82.7%, respectively at 120 min under 40 mA cm by Sn-Sb/PbO (PEG + Bi) electrode. The changes of biodegradability, biological toxicity and by-products were analyzed. Furthermore, 3,5-dimethylphenol was used as characteristic pollutant to study the degradation mechanism of phenolic pollutants in electrocatalytic system. According to the intermediate products detected by GC-MS, possible degradation pathways in electrocatalytic system were proposed.