As a promising anode material for sodium-ion batteries, MoS2 unfortunately suffers from its poor electrical/ionic conductivity and drastic volume variation during the repeated sodiation/desodiation, which lead to unsatisfied rate capability and cycleability. Herein, we employ popcorn, an environment benign biomass, as carbon source to construct MoS2/popcorn-derived carbon composites. The composite processes a sandwich-like structure due to the intercalation of carbon, realizing sufficient contact of MoS2 monolayers with carbon as well as expanded interspace of (002) layers in MoS2. The sandwiched structure facilitates electronic transfer as well as Na+ diffusion, and is robust to the volume variation during the sodiation/desodiation. As an anode material for sodium-ion batteries, the optimized composite displays a reversible capacity of 475 mAh g−1 at 0.2 A g−1 in the initial cycle, and maintains 406.9 mAh g−1 after 340 cycles. When coupled with NaV0.9Fe0.1PO4 in full sodium-ion batteries, the composite delivers a reversible capacity of 278.4 mAh g−1 in the voltage range of 1.0–3.2 V at 1 A g−1, indicating its practical application for sodium-ion batteries.