Aqueous Sn‐air batteries are attracting a great deal of interest in recent years due to the ultra‐high safety, low cost, dendrite‐free and highly reversible Sn anode. However, the slurry oxygen reduction/evolution reaction (ORR/OER) kinetics on the air cathodes seriously affect the Sn‐air battery performances. Although various advanced catalysts have been developed, the charge overpotentials (~1000 mV) of these Sn‐air batteries are still not satisfactory. Herein, iron oxide (Fe2O3) modified titanium dioxide (TiO2) nanorods with heterogeneous structure are firstly synthesized on Ti mesh (Fe2O3@TiO2/Ti), and the obtained Fe2O3@TiO2/Ti is further applied as catalytic electrodes for Sn‐air batteries. The core‐shell heterogeneous structure of Fe2O3@TiO2/Ti can effectively facilitate the conversion of electrochemical intermediates and separation of photo‐excited electrons and holes to active oxygen‐related reaction processes. DFT and experimental results also confirm that Fe2O3@TiO2/Ti can not only act as the electrocatalysts to improve ORR/OER properties, but also exhibit the superior photo‐catalytic activity to promote charge kinetics. Hence, the Fe2O3@TiO2/Ti‐based Sn‐air batteries show ultra‐low overpotential of ~40 mV, excellent rate capability and good cycling stability under light irradiation. This work will shed light on rational photo‐assisted catalytic cathode design for new‐type metal‐air batteries.