The complexity and expense of manufacturing all-solid-state batteries have long hindered the development of large-scale all-solid-state batteries for transportation and grid storage applications. Key issues include electrolyte-electrode interfacial resistance, air and moisture stability, and mass production capabilities. In this work, we propose a new battery manufacturing method which overcomes the challenges in interfacial resistance and scalability by using synchronized electrospinning and electrospraying. This method enables layer-by-layer depositing of cathode, solid-state electrolyte, and anode layers directly on top of one another. Herein, a LiFePO4 cathode and a Tin (Sn) anode have been selected to create for the first time a proof of concept all-solid-state lithium-ion battery in a full-cell configuration by using the synchronized electrospinning and electrospraying technique. This electrospinning and electrospraying synchronized technique created a poly(ethylene oxide)-based electrolyte, which demonstrates a conductivity of ∼1⋅10−5 at room temperature and ∼1⋅10−3 S cm−1 at 60 °C. Using the air-stable electrolyte and electrode materials, the synchronized electrospinning and electrospraying technique enables manufacturing of all-solid-state batteries in an ambient environment with reversible electrodes outlined in this work. Furthermore, the approach could ensure a straightforward transition to a roll-to-roll process and incorporate a wide range of materials for future large-scale manufacturing.