Solid polymer electrolytes (SPEs) hold the potential to revolutionize energy storage by enabling secondary batteries containing lithium metal anodes, which have ultra-high theoretical capacity of 3860 mAh g−1, compared to a typical graphite anode’s theoretical capacity of 372 mAh g−1. The bulk of SPE research focuses on optimizing SPE chemistry, while the manufacturing process receives little attention. In this interdisciplinary study, as shown in Figure 1, an electric-field-assisted ultrasonic spray pyrolysis (EFAUSP) setup is proposed and integrated with a cyclone-separator, which was simulated ANSYS Fluent, then built based on the results. Digital in-line holography is performed to determine the droplet size distribution and investigate the droplet trajectories near the substrate surface. This newly proposed EFAUSP setup is based on a 3D printer controller, promising macrostructure and microstructure control in future work. Future work will build upon these results to investigate the mechanical and electrochemical properties of the deposited SPEs.