In this work, monolithic zinc oxide/bismuth oxychloride/graphite oxide/polyvinylidene fluoride (ZnO/BiOCl/GO/PVDF) composite membrane was prepared by immersion precipitation phase transition method. The photocatalytic degradation performance of the composite membrane was verified by using methylene blue (MB), rhodamine (RhB) and tetracycline (TC) as target pollutants, and the composite membrane was tested by XRD, SEM and other testing methods. The results show that the thin sheet structure of bismuth oxychloride (BiOCl) provides more active sites, the fold-like structure of graphene oxide (GO) facilitates the adhesion of ZnO, which contributes to the improvement of photocatalytic effect. Meanwhile, ZnO combines with BiOCl to form p-n heterojunction structure, expanding the visible light response range of the composite material. Under the irradiation of visible light, the removal rate of RhB reaches 95.5% at 180 min, and the removal rate of TC reaches more than 93.1% at 140 min, which can achieve the basic removal of pollutants. The degradation rate of MB by the composite membrane still reaches 97.8% after 5 times of recycling. Under the background of “double carbon”, the monolithic ZnO/BiOCl/GO/PVDF composite membrane prepared in this work can be used as an environmentally friendly, stable and economical photocatalyst for the removal of water-soluble pollutants such as MB, and the composite membrane has a broad application prospect in the degradation of water-soluble pollutant wastewater by monolithic catalyst.