Adhesion of Li plating to electrode substrate and chemical stability of plated Li against electrolyte components are two essential factors affecting the cycling performance of Li metal in a rechargeable Li battery. Poor adhesion results in high contact resistance and further the formation of dead Li. Aiming to improve the adhesion of Li plating to Cu substrate, we plate a very thin tin layer as the primer for Li plating on the Cu substrate. By this way, Li metal is first reacted with tin to form a Li-Sn alloy, and then Li is cycled on resultant Li-Sn alloy so that the Li-Sn alloy functions as an “electric glue” to electrically connect the Li plating and Cu substrate. Attributed to the strong affinity between Li and Li-Sn alloy, the pre-plated tin layer is shown not only to enhance the adhesion of the plated Li to electrode substrate but also to improve the morphology of Li plating. Using a 1.0 m (molality) LiPF6 1:4 (wt.) fluoroethylene carbonate/ethylmethyl carbonate electrolyte, in this paper the effect of the tin primer layer on the Li cycling performance in a Li/Cu cell and a Cu/LiNi0.85Co0.10Al0.05O2 cell is demonstrated and discussed.