The combination of graphite or silicon monoxide (SiO)/graphite=1/1 mixture with a solvent-free solid polymer electrolyte (SPE) was fabricated using a new preparation process, involving precoating the electrode with vapor-grown carbon fiber (VGCF) and binders (polyvinyl difluoride: PVdF or polyimide: PI), followed by the overcoating of the SPE. The reversible capacity of [graphite | SPE | Li] and [SiO/graphite | SPE | Li] cells were >360 and >1000mAhg−1 with 78% and 77% for the 1st Coulombic efficiency, respectively. The reversible capacities were 75% at the 250th cycle for [graphite | SPE | Li] and 72% at the 100th cycle for [SiO/graphite | SPE | Li]. The electrode used was compatible with that of the conventional liquid electrolyte system, and the SPE film could be formed on the electrode by the continuous overcoating process, which will lead to a low-cost electrodes and low-cost battery production. The solid-state lithium-ion polymer battery (SSLiPB) developed in this study, which consisted of [LiFePO4 | SPE | graphite], showed the reversible capacity of 128mAhg−1 (based on the LiFePO4 capacity) with favorable cycle performance.