The room temperature (RT) sodium–sulfur batteries (Na–S) hold great promise for practical applications including energy storage and conversion due to high energy density, long lifespan, and low cost, as well based on the abundant reserves of both sodium metal and sulfur. Herein, freestanding (C/S/BaTiO3)@TiO2 (CSB@TiO2) electrode with only ≈3 wt% of BaTiO3 additive and ≈4 nm thickness of amorphous TiO2 atomic layer deposition protective layer is rational designed, and first used for RT Na–S batteries. Results show that such cathode material exhibits high rate capability and excellent durability compared with pure C/S and C/S/BaTiO3 electrodes. Notably, this CSB@TiO2 electrode performs a discharge capacity of 524.8 and 382 mA h g−1 after 1400 cycles at 1 A g−1 and 3000 cycles at 2 A g−1, respectively. Such superior electrochemical performance is mainly attributed from the “BaTiO3‐C‐TiO2” synergetic structure within the matrix, which enables effectively inhibiting the shuttle effect, restraining the volumetric variation and stabilizing the ionic transport interface.