The surface of LiFePO4/C cathode material is coated with nano-sized Sn via a simple electroless deposition (ED) process, and the effects of the Sn-coating on the electrochemical performances of LiFePO4/C are investigated systematically by the charge/discharge testing, cyclic voltammograms and AC impedance spectroscopy, respectively. In comparison with the pristine LiFePO4/C, the Sn-coated LiFePO4/C exhibits higher capacity, better cyclability and higher rate capability in a wide operation temperature range. An analysis of the electrochemical measurements reveals that Sn-coated LiFePO4/C has good electric contact among particles, much lower charge-transfer resistances and higher lithium diffusion rate, especially at low temperature. In addition, the Sn-coating layer protects the active materials from chemical attack by HF and thus suppresses the dissolution of Fe from LiFePO4 in the LiPF6 based electrolyte.