BiOBr/TiO2 nanotube arrays (TNAs) photoanodes were prepared via a two-step method. The microstructure and performance were investigated. BiOBr/TNAs with 15 deposition cycles showed the highest activity and thus worked as photoanode to construct a photocatalytic fuel cell (PFC). Compared with a single photoanode, BiOBr/TNAs-Pt PFC improved photocatalytic activity due to better separation of photoexcited holes and electrons, and exhibited superior simultaneous electricity generation ability. Besides, the working mechanism of PFC was illustrated to clarify the photocatalytic reactions in detail.