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A novel hybrid system composed of a photocatalytic fuel cell (PFC) and Fenton reactor was developed with the aim to degrade the azo dye Reactive Black 5 (RB5) and generate electricity. Compared to previously established system of bioelectro-Fenton system, microbial fuel cell (MFC) system has significant challenge in the development and operation system. Therefore, PFC is used instead of MFC to generate electrons for the Fenton system. The effect of azo dye (RB5) on each PFC and Fenton reactor was investigated. The experimental results showed that maximum power output was achieved in the absence of dye in the Fenton reactor of this hybrid system. Furthermore, higher degradation efficiency of RB5 could also be observed in the PFC reactor in this hybrid system.