AbstractEmerging photoelectrocatalysis (PEC) systems synergize the advantages of electrocatalysis (EC) and photocatalysis (PC) and are considered a green and efficient approach to CO2 conversion. However, improving the selectivity and conversion rate remains a major challenge. Strategies mimicking natural photosynthesis provide a prospective way to convert CO2 with high efficiency. Herein, several typical strategies are described for constructing biomimetic photoelectric functional interfaces; such interfaces include metal cocatalysts/semiconductors, small molecules/semiconductors, molecular catalysts/semiconductors, MOFs/semiconductors, and microorganisms/semiconductors. The biomimetic PEC interface must have enhanced CO2 adsorption capacity, preferentially activate CO2, and have an efficient conversion ability; with these properties, it can activate CO bonds effectively and promote electron transfer and CC coupling to convert CO2 to single‐carbon or multicarbon products. Interfacial electron transfer and proton coupling on the biomimetic PEC interface are also discussed to clarify the mechanism of CO2 reduction. Finally, the existing challenges and perspectives for biomimetic photoelectrocatalytic CO2 reduction are presented.