Tin hexaferrite (SnFe 12 O 19 ) nanostructures with functionalized multi-walled carbon nanotubes (MWCNTs) are prepared using a novel sol-gel autocombustion method. The synthesis process is accomplished by reaction between tin chloride and iron (III) nitrate in water, in the presence of a green compound as capping, fuel and reducing agent. The products are characterized by different techniques containing FT-IR, XRD, EDX, FE-SEM, BET and CV. Then, the hydrogen storage performance of the nanostructures is electrochemically investigated in alkaline media. The electrochemical data exhibit that the SnFe 12 O 19 nanocomposite (SnFe 12 O 19 /MWCNTs) shows high capacity for hydrogen storage, excellent reversibility and rate dischargeability in atmospheric pressure and temperature. The maximum discharge capacity of SnFe 12 O 19 /MWCNTs nanocomposite is obtained 360 mAh/g in first cycle and improved to 2050 mAh/g after 15 cycles. This significant storage capacity for hydrogen can be ascribed to its hierarchical architecture, which leads to improving the surface area, decreasing the diffusion pathway and buffering the volume change during cycling.