Herein, a novel type-II BiVO4/BiOI (BVOI) heterojunction electrode material was successfully fabricated by using a facile two-step electrodeposition approach. The experimental results revealed that BiOI nanosheets were deposited onto the surface of BiVO4 particles successfully, with the special morphology providing more active sites, which was beneficial to the improvement of PEC performance. According to the electrochemical performance tests, it could be observed that the construction of a heterojunction effectively promoted the separation of photoinduced electron-hole pairs and increased the transfer rate of surface charges. Under visible-light irradiation, the BVOI-300 photoanode possessed the highest PEC β-naphthol degradation rate at pH = 7, which approximately reached 82%, whose corresponding kinetic constant was 1.4 and 1.5 times higher than those of pure BiVO4 and BiOI. After five cycles, the degradation rate still remained at 64.61%. The band structure of the BVOI electrode was deduced, and the PEC mechanism of the BVOI electrode was investigated through the radical trapping quenching experiments and ESR test, which indicated that the ˙OH, h+ and ˙O2- radicals were crucial active species in the PEC β-naphthol degradation process. For the BVOI-300 working electrode, the TOC content of coal gasification wastewater (CGW) decreased from 94.44 to 54.4 mg L-1, and the removal rate reached 42.4%. GC-MS was used to identify the organic components of coal gasification wastewater, which was expected to provide reference for remedying actual gasification wastewater containing refractory organic pollutants and offer a new development direction for the treatment of actual coal chemical wastewater.