An all solid-state lithium/polypyrrole (PPy) battery using polyethylene oxide (PEO)-LiClO4 as a solid polymer electrolyte was assembled, and the effects of the morphology of the PPy film and the concentration of LiClO4 on battery performance were investigated. Optimum conditions for the redox properties of PPy films in PEO-LiClO4 at 80-degrees-C were obtained with an LiClO4 concentration of n = 8 - 20 (n=[EO]/[Li]) when using rough PPy film. A Li/PPy battery using PEO-LiClO4 with optimized conditions exhibited high coulombic efficiency, above 90% at 0.1 mA cm-2 at 80-degrees-C. Cyclability of 1400 cycles with high coulombic efficiency was attained.