The quartz crystal microbalance (QCM) was used to investigate the formation of surface films on a lithium anode. Whereas few studies have dealt directly with electrode mass changes, QCM was employed here to investigate in situ the deposition and dissolution of lithium on a Ni substrate, with respect to mass changes and changes in the surface‐film morphology. The formation and destruction of the deposited surface film was followed by a real‐time measurement of the resonance frequency (Δf) and the resistance parameter (ΔR). ΔR expresses the energy loss to the oscillation of the crystal at resonance state, which gave us useful information on the variation of surface roughness during charge‐discharge cycles. The Δf and ΔR variations are discussed for three different electrolyte systems, viz, , and in propylene carbonate or diethyl carbonate solutions. Upon cycling, Δf showed an irreversible decrease indicating continuous formation and destruction of the surface film. The extent of Δf shift depended strongly on the electrolyte being larger for /PC and /PC systems than that for /PC. The ΔR measurement indicated a smoother and more uniform surface of the deposited lithium for /PC compared to those for /PC and /PC. In the /PC system, the mass was found to increase even during the initial dissolution process. Such behavior can be explained by a healing process involving the subsequent chemical formation of a surface film right after dissolution of lithium. This process is faster than the lithium dissolution process itself in this case.