Li‐O2 batteries (LOBs) have garnered significant attention in recent years due to high theoretical specific capacity, however, the sluggish charge‐discharge reaction kinetics and rapid failure under high current densities have hindered their further application. This work presents a photo‐responsive catalyst (UIO‐66‐NH2) supported on carbon cloth, which could enhance the reaction kinetics of LOBs and improve the discharge capacity under high current densities. It demonstrates that under light, the overpotential decreases by 0.9 V, and the discharge capacity reaches an impressive 4.8 mAh cm‐2 at a current density of 0.5 mA cm‐2. This finding is expected to inspire the development of various novel MOF‐based photoelectrodes for LOBs.