All-solid-state thin-film lithium-ion batteries are important in the development of next-generation energy storage devices with high energy density. However, thin-film batteries have many challenges in their manufacturing procedure. This is because there are many factors, such as substrate selection, to consider when producing the thin film multilayer structure. In this study, we compare the fabrication and performance of all-solid-state thin-film lithium-ion batteries with a LiNi0.5Mn1.5O4 cathode/LiPON solid electrolyte/ Li4Ti5O12 anode structure using stainless steel and Si substrates with different surface roughness. We demonstrate that the smoother the surface of the substrate, the thinner the thickness of the all-solid-state thin-film lithium-ion battery that can be made, and as a result, the corresponding electrochemical characteristics can be improved.