A conductive polymer shell with electron collection behavior is constructed on an S. oneidensis MR-1/CdS inorganic−biohybrid photocatalytic system, which endows the engineered cells with the capability of excellent conductivity and broad visible-light absorption, and thus, the transport of photogenerated electrons at the biotic and abiotic interfaces is promoted, achieving efficient hydrogen production (23.18 μmol 10 9 cells −1 day −1 ) for over 15 days compared with the traditional organic diffusion electron medium. A practical application was also conducted by using wastewater and natural sunlight for the hydrogen production, and 92.67 μmol of hydrogen was generated from the hybrid system within 7 days under wastewater and sunlight. This study contributes a new method for optimizing the interfacial electron transfer of inorganic−biohybrid systems for their application in the field of green energy production and provides insight into the rational design of the whole-cell biohybrid system with various production of valuable chemicals.