A photoinduced flexible Li‐CO2 battery with well‐designed, hierarchical porous, and free‐standing In2S3@CNT/SS (ICS) as a bifunctional photoelectrode to accelerate both the CO2 reduction and evolution reactions (CDRR and CDER) is presented. The photoinduced Li‐CO2 battery achieved a record‐high discharge voltage of 3.14 V, surpassing the thermodynamic limit of 2.80 V, and an ultra‐low charge voltage of 3.20 V, achieving a round trip efficiency of 98.1 %, which is the highest value ever reported (<80 %) so far. These excellent properties can be ascribed to the hierarchical porous and free‐standing structure of ICS, as well as the key role of photogenerated electrons and holes during discharging and charging processes. A mechanism is proposed for pre‐activating CO2 by reducing In3+ to In+ under light illumination. The mechanism of the bifunctional light‐assisted process provides insight into photoinduced Li‐CO2 batteries and contributes to resolving the major setbacks of the system. [ABSTRACT FROM AUTHOR]