ABSTRACT Polymer‐dispersed liquid crystals (PDLC) have emerged as a promising solution for smart windows due to their ability to switch between opaque and transparent states when subjected to an electric field. However, traditional PDLC often encounters challenges such as high driving voltages, slow response times, and poor optical clarity, which limit their practical applications. In this study, we propose a molecular engineering strategy to modify the structure of polymerizable monomers, optimizing the microstructure of the polymer film and thereby enhancing its electro‐optical performance. Additionally, the film demonstrates excellent light modulation ability in the solar range, with transmittance values of T lum = 76.73% and T sol = 66.88%. Furthermore, due to the abundant chemical bonds within the film and its microporous structure, it exhibits a high emissivity of approximately 91% in the atmospheric window (8–13 μm). Sunlight simulation tests indicated that the indoor temperature decreased by 5°C compared with ordinary glass during the same exposure period. MATLAB simulations revealed that the maximum cooling power reached 60.17 W/m 2 /K during the daytime and 109.63 W/m 2 /K at night. This work provides valuable insights and ideas for the development of energy‐efficient and environmentally friendly smart windows.