The urban heat island (UHI) is a major environmental hazard due to its impact on energy demand, air pollution, heat-related mobility, and mortality. In this regard, incorporating cool materials to reduce the temperature of urban surfaces is an effective approach. Nevertheless, adopting this technology contributes to an overcooling penalty in the winter season. Thermochromic materials are an alternative mitigation technique because of their all-season thermal regulation capability. This study examined the optical behavior of a thermochromic multilayer coating (TCMLC) under various temperature conditions to examine its cooling and heating potential. The samples were characterized through spectrophotometry and infrared thermography analysis. A dynamic temperature-controlled device was used to control the surface temperature. The TCMLC exhibits a low solar reflectance (0.11) in a colored state; however, it demonstrates a noticeable initial upward trend in the near-infrared spectrum (NIR); in addition, a high thermal emittance (0.95) was observed in this state. Regarding the effectiveness of its passive cooling potential, in its colorless state the TCMLC showed an initial solar reflectance of 0.48, with an increasing trend after 700 nm; this can be counterbalanced by a significant thermal emittance value of 0.87 in the range of 8 to 14 μm. The easy and scalable application of this coating makes it competitive for low-income and heat-vulnerable areas; therefore, further research is necessary to assess the material's thermal performance in built-environment applications.