Room-temperature sodium-sulfur (RT Na-S) batteries have been attracting enormous interests due to their low-cost, high capacity and environmental benignity. However, the shuttle effect and the sluggish electrochemical reaction activity of sodium polysulfides (NaPSs) seriously restrict their practical application. To solve these issues, we rationally designed an advanced Sn-doped In2S3/S/C cathode for RT Na-S batteries by magnetron sputtering in this work, which exhibited a high reversible capacity (1663.5 mAh g-1 at 0.1 A g-1) and excellent cycling performance (902.9 mAh g-1 after 50 cycles). The in situ electrochemical impedance spectroscopy indicated that the Sn-doped In2S3 coating can accelerate charge-transfer kinetics and facilitate the diffusion of Na+. Furthermore, theoretical calculation revealed that doping of Sn into In2S3 can reduce the energy band gap, thus accelerating the electron transfer and promoting the electrochemical conversion of active species. It is demonstrated that adjusting the electronic structure is a reliable method to improve the electrocatalytic effect of catalyst and significantly improve the performance of S cathode in RT Na-S batteries.