Tin nano-array electrodes were assembled by electrochemical deposition using alumina anodic oxide (AAO) as templates. Morphology and structure of the tin electrodes were characterized by SEM and XRD. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were applied to reveal the electrochemical performance of the electrodes used as anode of Li-ion battery. Compared to electrodes of tin film and tin foil from rolling, the electrodes of tin nano-arrays are very active. The EIS spectra of tin nano-array electrodes show different characters from electrodes of tin film and tin foil. A medium-frequency area has been found which is ascribed to the large charge transfer area across the electrode/electrolyte interface. The lithium ion transporting in solid-electrolyte ion surface layer are controlled by structure of electrodes. The surface resistances for nano-arrays observed from high frequency ace are between 19.8 and 14.6 Ω·cm2. The highest diffusion coefficient is 10-10 cm2·s-1 for nano-array electrode, at potential of 0.2 V. The nano-array structure can lead to high electrochemical activity of the electrodes.