Due to the inherent mechanism limitation of photocatalytic fuel cell based self-powered biosensors (PFC-SPBs), it was difficult to distinguish the power density of various photoactive materials or recognition events in one detection process, which made it lack multitarget quantitative capacity. In order to solve this problem, we proposed an electron-transfer-regulated conversion strategy for the construction of multiplexed PFC-SPBs. Herein, the n-type CdS/Fe2O3 nanorod array (NR) heterojunction and p-type CuBr semiconductor were used as photoactive materials to prepare the photoanode and photocathode. Based on the appropriate Fermi level differentiation between these two photoelectrodes, a self-powered sensing platform driven by visible light without external energy supply was achieved. In this design, two kinds of common and easily coexisting mycotoxins OTA and AFB1 acted as model analytes. The coupling of "signal off" and "signal on" was realized by controlling the electronic transmission on the interface between the photoanode and photocathode, so as to achieve the simultaneous detection of two mycotoxins. This work established a proof-of-concept for the integration of a dual-photoelectrode with dual-assay that could provide the innovative inspiration for the formation of a general multiplexed self-powered sensing platform.