Solar-driven photocatalytic degradation of antibiotics has emerged as an eco-friendly approach to treating wastewater. And singlet oxygen is a selective and highly active reactive oxygen species. Bi2MoO6 microsphere photocatalyst modified by narrow band gap PDI organic supramolecular was prepared by water bath heating method to achieve the selective generation of non-free radical. It focused on the effects of different acid-induced assembled and different light sources on the photocatalytic performance of PDI/Bi2MoO6 (PDI/BMO) photocatalysts and explored their ability to remove various pollutants. The results showed that PDI/BMO composites self-assembled with nitric acid (1% PMN) could effectively purify a variety of pollutants under visible light irradiation, including CIP, TC, LVF and AO7. In addition, 1% PMN showed excellent photocatalytic performance in actual water, and even have fair degradation efficiency under red light irradiation. Holes and singlet oxygen were confirmed to be the main reactive oxygen species during CIP degradation by capture experiments and EPR, and the steady-state concentration of singlet oxygen was quantified. Three degradation pathways of CIP under the action of non-radicals were clarified, and the biotoxicity of CIP treated products was evaluated by bacteriostatic experiments. This work could provide an ecologically friendly method for wastewater treatment.