The cycling performance of a Li metal electrode in rechargeable Li batteries is studied using a novelly formed Li–Zn alloy as a substrate. A Zn layer electrodeposited on a Cu disk with ultrasonic assistance is used as a substrate precursor. Li electrodeposition followed to form the Li–Zn alloy. The morphologies of the substrate before and after Li deposition and stripping are investigated by scanning electron microscopy (SEM), and the electrochemical properties of the substrate are investigated by galvanostatic charge-discharge and cyclic voltammetry (CV). The growth states of solid electrolyte interface (SEI) films of Li deposits on the Li–Zn alloy and Cu surfaces are compared by electrochemical impedance spectroscopy (EIS); exchange current densities of Li electrodeposition on Cu, Zn, and Li–Zn alloy substrates are also compared based on tests of constant current pulse deposition. The efficiency of Li deposition/stripping on the Li–Zn alloy substrate remains high at 96.7% after 400 cycles at a current density of 0.1mAcm−2 and 250 cycles at the current density of 0.2mAcm−2. These results can be attributed to the formation of a stable SEI film on the Li–Zn substrate and the high exchange current density of Li deposition and stripping on this substrate. The Li–Zn alloy proposed in this work may be a perfect substrate for enhancing the cycling capability of Li metal electrode.