A new type of all-solid-state lithium-ion rechargeable batteries composed of LiMn2O4 positive and V2O5 negative electrodes were developed and their electrochemical characteristics were investigated for the first time. Both amorphous thin-filmed electrodes as well as a lithium phosphorus oxynitride electrolyte (Lipon) were deposited on a substrate by using a rf-magnetron sputtering method. The present rocking-chair type battery showed good charge and discharge characteristics with a typical charge and discharge capacities of about 18μAh/cm2 between 3.5 and 0.3V. This battery revealed a remarkable forming process which means that the charge and discharge capacities dramatically increase with the cycle number in its early stages. The battery also showed a good charge–discharge operation in vacuum which is one of the advantageous properties expected for the solid-state devices.