In this paper, we reported a highly thermal stable YP‐11 polymer stabilized cholesteric liquid crystal (YP‐11 PSCT) for smart windows that can be electrically switched from transparent to opaque. The polymerization between photo‐sensitive monomers (RM 257) has been characterized using a polarized optical microscope (POM), which has been found to become much firmer and denser by raising the doping concentration. The 3D polymer matrices remarkably affect the electro‐optical performances of YP‐11 PSCT, and the cholesteric liquid crystals (Ch LCs) within polymer matrices were found merely able to be reversibly switched until the doping concentration of RM 257 was raised up to 3%. Specifically, the threshold voltage, raising time and decaying time of a 3% YP‐11 PSCT cell were determined as 22.908 V, 85.442 ms and 18.617 ms, respectively. The critical thermal‐stable temperature of the 3% YP‐11 PSCT was further evaluated using a hot stage and was confirmed as high as up to 100 °C. These findings in this paper will significantly contribute to the development of smart windows.