The present invention relates to the technical field of wastewater treatment, and discloses a method for enhanced bio-treatment of refractory organic pollutants with photo-excited holes as electron acceptors. The method comprises the following steps: 1) placing a composite semiconductor-coated carrier material into a reactor, introducing wastewater into the reactor inoculated with anaerobic sludge, and allowing the composite semiconductor-coated carrier material to be immersed in the wastewater, wherein the composite semiconductor-coated carrier material comprises a conductive carrier and composite semiconductor materials loaded on the conductive carrier; 2) carrying out habituated culture on the anaerobic sludge for a period of time, and loading a biological membrane on the surface of the composite semiconductor materials, to construct a photo-excited hole enhanced bioreactor; and 3) treating the refractory pollutants in the wastewater by utilizing the reactor under irradiation.