The structure of the highly durable silicon-based anode prepared by electrodeposition was investigated for volume change and chemical structure. With repeated charge–discharge cycles, the volume change resulting from the anode film thickness decreased, and, after 100 cycles, essentially no difference was observed between the charged and discharged states. The buffering effect of the volume change was considered to be achieved by the formation of Li2O, Li2CO3, and lithium silicates such as Li4SiO4, whose existence were supported by STEM, EELS, and XPS analyses. From the structural analyses, the main reactions related to the capacity of the silicon-based anode were considered to be the formation of Li x Si and Li2Si2O5. Li x Si and Li2Si2O5 can be delithiated into Si and SiO2, respectively.