In this study, a graphene-based dual-photoelectrode photocatalytic fuel cell (PFC) system, incorporating n-type ZnO photoanode and p-type Cu2O photocathode, has been meticulously designed and fabricated to achieve concurrent organic pollutant decomposition and electricity production. The rGO-ZnO|rGO-Cu2O PFC system displayed superior photoelectrocatalytic performance, surpassing the comparative FTO-based PFC system. Notably, it achieved power density of 22.23 μW cm−2 maximumly, tetracycline hydrochloride (TCH) degradation efficiency of 74.0 % within 120 min, and exhibited long-term stability. This enhanced performance can give the credit to the larger active areas generated by the in-situ growth of photocatalytic materials in layered microstructure of graphene films, as well as the rapid electron transfer within graphene films. This study underscores the potential application of graphene films as electrode substrate materials, and introduces a strategy for achieving the diversification and optimization of electrode substrate material selection, ultimately facilitating the development of more efficient PFC systems.