A major challenge for the implementation of intact bacterial cells in photo‐bioelectrochemical systems remains the hindered extracellular electron transfer. This study focuses on purple bacteria, photosynthetic microorganisms particularly interesting for the development of bioelectrochemical systems because of their versatile metabolisms. Although soluble monomeric redox mediators have been proven as effective systems for electron transfer mediation, their application in the field is not preferable owing to their toxicity and unwanted release into the environment. An abiotic/biotic photoanode is reported in which a bioinspired redox mediating system is implemented in a 3D geometry allowing to “electrically wire” intact bacterial cells. The 3D photoanode decreased the overpotential required for harvesting photoexcited electrons, operating at +0.073 V versus the saturated calomel electrode (SCE). Accordingly, the overpotential was significantly reduced compared with a pioneering Os‐redox polymer reported in literature, which required operation at +0.303 V versus SCE. These results provide the basis for further development of bio‐photoanodes for light‐powered biosensing and power generation.
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