A visible-light responsive photocathode microbial electrosynthesis (MES) is an attractive method for CO 2 fixation via a microbial electrochemical process. Here, an α-Fe 2 O 3 /g-C 3 N 4 formed a Z-scheme heterojunction structure and exhibits high photogenerated electron−hole separation ability under visible light. The low valence band potential of α-Fe 2 O 3 makes binding electrons transferred from the anode easier for photogenerated holes, providing an additional driving force to improve MES performance. Furthermore, the introduction of α-Fe 2 O 3 can promote electron transfer between the electrode and microorganisms. α-Fe 2 O 3 /g-C 3 N 4 achieved an acetate production rate of 0.33 g L −1 d −1 , which increased by 3-fold compared to a carbon felt cathode. This work provides new opportunities for constructing a highly efficient photocathode for MES. KEYWORDS: Microbial electrosynthesis, α-Fe 2 O 3 /g-C 3 N 4 , Photocathode, Electron transfer