Cu–MOF was obtained by a facile aqueous room temperature synthesis method, and Cu–C was prepared by using Cu–MOF as a sacrificial template. The ultrafine SnOx nanoparticles were loaded onto Cu–C by a pyrolysis process to form SnOx/Cu–C. Cyclic voltammetry and galvanostatic charge/discharge were employed to examine the electrochemical properties of the as-synthesized composite. Benefiting from the excellent conductivity of Cu, the ultra-fine size of nanoparticles, the unique structure derived from MOF and the synergistic effect between SnOX and Cu–C, SnOX/Cu–C electrode exhibited an exceptional electrochemical property. A high charge specific capacity of 649 mA h g−1 can be reached even at a current density of 2000 mAg−1. The reversible capacity is maintained at 668 mA h g−1 at 1000 mA g−1 after 300 cycles. The results indicate that the material may be considered as a promising anode candidate for lithium-ion batteries.