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In this paper, a polymer dispersed liquid crystal (PDLC) film with good electro-optical properties and wide working temperature range was prepared by the UV-polymerization induced phase separation (PIPS) method by optimizing the curing temperature using a LC with wide temperature range. The investigation found that when the polymerization temperature was at the clearing point of the prepolymer/LC mixture, the film had better electro-optical properties and a high contrast ratio of 51 at 90 °C, and the rise time and decay time were respectively as fast as 241.5 ms and 1750 ms at −20 °C. This study provides further methodological guidance for the curing process of PDLC film, and promotes its application in outdoor smart windows.