VO2-based thermochromic coatings have gained much attention in temperature-adaptive smart windows, and constructing multilayer film structures is the main way to obtain high thermochromic performances. Based on the self-developed objective-orientated automatic optimization code, the present research realized customized designs of thermochromic multilayer coatings composed of VO2, TiO2, and SiO2 from the objectives of visible luminance (Tlum) and solar light modulation (ΔTsol). The TiO2/VO2/s, VO2/TiO2/s, TiO2/VO2/TiO2/s, and SiO2/TiO2/VO2/TiO2/s (s denotes substrate) multilayer film systems were then prepared by magnetron sputtering and vacuum controllable heating, with their structures, insulator-metallic transition, and thermochromic properties being carefully studied. The result showed that the best trade-off between high Tlum and high ΔTsol was achieved for these film assemblies, and solar light modulation was mainly limited at the near-IR wavelength region of the solar spectrum, with the difference between cool- and hot-state Tlum being greatly reduced. In the case of the four-layer SiO2/TiO2/VO2/TiO2/s, very high average Tlum (60%) and high ΔTsol (14%) were obtained. A 100 × 100 mm2 of the SiO2/TiO2/VO2/TiO2/s was also prepared, and it showed an obvious temperature adjustment, and the service life can last for 14 years under normal weather conditions. Not limited to the prepared multilayer film systems, the methodology used here is also suitable for the fast development of other multilayer film systems.