Sodium-ion batteries have attracted extensive interest for energy storage and conversion as an alternative to lithium-ion batteries. The development of advanced electrode materials is important for the implementation of sodium-ion batteries into practical applications. Herein, we developed a facile soaking-chemical vapour deposition method to grow core–sheath structured Sn@CNT nanopillar arrays on carbon paper with a unique 3D hierarchical architecture as free-standing electrode for sodium-ion batteries. The electrode achieved a reversible capacity of 887µAhcm−2 in the first cycle and good cyclability extending to 100 cycles. The electrode also demonstrated a promising rate capability, which is suitable for high power applications. We also assembled prototype Na-ion full cells, consisting of the as-prepared free-standing Sn@CNT@carbon paper anode and Na0.80Li0.12Ni0.22Mn0.66O2 cathode. The full sodium-ion battery can power LED lights. This work is expected to inspire the development of sustainable sodium-ion batteries for energy storage and conversion.