The effect of VC as electrolyte additive on the electrochemical performance of Si film anode was studied in this paper. The charge/discharge test, scanning electron microscopy (SEM), electrochemical impedance spectrum (EIS), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to investigate the cycle performance and SEI layer of Si film anode. It was found that the SEI layer formed in VC-containing electrolyte possessed better properties. It was impermeable to electrolyte and its impedance kept almost invariant upon cycling. The presence of VC in electrolyte brought out the VC-reduced products and decreased the LiF content in SEI layer. The major components of SEI layer were similar in VC-free and VC-containing electrolytes, which contained lithium salt (e.g. ROCO2Li, Li2CO3, LiF), polycarbonate and silicon oxide. It was newly found that silicon oxide could be formed in SEI layer of Si film anode due to the reaction of lithiated silicon with permeated electrolyte in both VC-free and VC-containing electrolytes.