In this work, 1,4-dioxane (cyclic ether ) was used to pre-treat the surface of Li electrode in order to passivate Li electrode and improve its interfacial stability and charge/discharge cycleability. It Is found that 1,4-dioxane can polymerize and form a good SEI passivating layer on the surface of Li electrode. This layer is able to enhance the interfacial stability of Li electrode without depress its kinetic behavior. Further measurements of charge/discharge efficiency of treated/bare Li electrodes and cycleability of Li metal cells fabricated with different Li anodes show that the Li electrode treated with 1,4-dioxane has higher charge/discharge efficiency compared with that of bare Li electrode, and the cell with such anode has better discharging performance and cycle life.