Coal tar wastewater is hard to degrade by traditional methods because of its toxic pollutant constituents and high concentration of aromatic hydrocarbons, especially phenolic substances. A new type of hydrophobic benzacetone modified PbO anode (BA-PbO electrodes) was used for the electrocatalytic treatment of coal tar wastewater in a continuous cycle reactor. The surface morphology, structure, valences of elements, hydrophobicity, hydroxyl radical (·OH) produced capacity, electrochemical properties and stability of BA-PbO electrodes were characterized by SEM (scanning electron microscopy), XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy), contact angle, a fluorescence probe test, an electrochemical workstation and accelerated life test, respectively. The BA-PbO electrodes exhibited a compact structure and finely dispersed crystallize size of 4.6 nm. The optimum degradation conditions of coal tar wastewater were as follows: current density of 90 mA cm, electrode gap of 1 cm and temperature at 25 °C with flow velocity of 80 L h. The chemical oxygen demand (COD) removal efficiency reached 92.39% after 240 min of degradation under the optimized conditions and the after-treatment COD value was 379.51 mg L which was lower than the centralized emission standard (less than 400 mg L). These findings demonstrated the feasibility and efficiency of electrocatalytically degrading coal tar wastewater by BA-PbO electrodes. The possible mechanism and pathway for phenol a specific pollutant in coal tar wastewater were investigated by quantum chemistry calculations (Multiwfn) and gas chromatography-mass spectrometry (GC-MS). The toxicity of each intermediate was predicted by the ECOSAR program.