Lithium metal electrode is pretreated with 1,3-dioxolane or 1,4-dioxane to improve its properties. The components and morphology of the surface films formed in the above two pretreatment liquids are studied using FTIR and SEM respectively. Li–LiCoO2 coin cells are then fabricated and their cycle and discharge performance are tested. It is found that the battery performance is greatly improved by such pretreatment. Interestingly, the 1,4-dioxane pretreatment is more effective than 1,3-dioxolane in improving the lithium metal electrode performance. To explore the mechanism(s) behind, the electrochemical impedance spectroscopy (EIS) is employed and an equivalent circuit model is designed for EIS analysis. The fitting curves are aligned well with the experimental curves, suggesting that the proposed equivalent circuit model is an ideal model for lithium battery. Next, the corresponding relationship between the impedance components and every individual semicircle in the Nyquist curves is inferred theoretically and the result is satisfying. Based on the analysis using this model, we conclude that the structural stability of SEI film is increased and the interfacial compatibility between the lithium substrate and the SEI film is improved by 1,3-dioxolane or 1,4-dioxane pretreatment.