Sn/Li 2 O composite coatings on stainless steel substrate, as anodes of thin-film lithium battery are carried out in SnCl 2 and LiNO 3 mixed solutions by using cathodic electrochemical synthesis and subsequently annealed at 200°C. Through cathodic polarization tests, three major regions are verified: (I) O 2 +4H + +4e − →2H 2 O (∼0.25 to −0.5V), (II) 2H + +2e − →H 2 , Sn 2+ +2e − →Sn, and NO 3 − +H 2 O+2e − →NO 2 − +2OH − (−0.5 to −1.34V), and (III) 2H 2 O+2e − →H 2 +2OH − (−1.34 to −2V vs. Ag/AgCl). The coated specimens are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and charge/discharge tests. The nano-sized Sn particles embedded in Li 2 O matrix are obtained at the lower part of region II such as −1.2V, while the micro-sized Sn with little Li 2 O at the upper part, such as −0.7V. Charge/discharge cycle tests elucidated that Sn/Li 2 O composite film showed better cycle performance than Sn or SnO 2 film, due to the retarding effects of amorphous Li 2 O on the further aggregation of Sn particles. On the other hand, the one tested for cut-off voltage at 0.9V (vs. Li/Li + ) is better than those at 1.2 and 1.5V since the incomplete de-alloy at lower cut-off voltage may inhibit the coarsening of Sn particles, revealing capacity 587mAhg −1 after 50 cycle, and capacity retention ratio C50/C2 81.6%, higher than 63.5% and 49.1% at 1.2 and 1.5V (vs. Li/Li + ), respectively.