Redox mediators can catalyze and accelerate the biodegradation of azo dyes, but they are easily lost in water. The immobilization of the redox medium on membrane provides a new idea for research. In this paper, a redox mediator membrane (AQS-RGO/PVDF) was prepared by phase inversion method using poly(vinylidene fluoride) (PVDF) as polymer and quinone-based graphene oxide (AQS-RGO) as redox medium to explore the catalytic performance of membrane for the biodegradation of azo dyes. The membranes were characterized by XRD and X-ray photoelectron spectroscopy (XPS), and the results show that AQS-RGO was successfully immobilized on the membrane. The structure and morphology of the membrane were characterized by SEM and atomic force microscopy (AFM), and the results show that the addition of the AQS-RGO mediator makes the spongy pores in the membrane denser. Moreover, the contact angle, water flux and rejection of the membrane were measured. It is found that the addition of AQS-RGO made the membrane has better hydrophilicity and permeability, and the maximum pure water flux is 283.09 L/(m2?h), which is 4.7 times higher than that of the original PVDF membrane. The AQS-RGO/PVDF membrane prepared under the optimal condition can shorten the degradation time (decolorization rate ≥90%) of reactive red X-3B from 48 h to 30 h, indicating that it has a good catalytic effect on the biodegradation of azo dyes. In addition, it can maintain a decolorization rate of more than 90% in 4 cycles of reactive red and acid red dyes. The redox medium membrane has a good stability, showing the application potential of the membrane.