Abstract Recently, smart windows based on polymer‐dispersed liquid crystals (PDLCs) composites have garnered enormous interest owing to their electrically switchable properties. However, the low UV‐shielding characteristics of these films limit their widespread application. Here, we reported novel PDLC composite films doped with functionalized TiO 2 nanoparticles (NPs) to enhance the UV‐shielding efficiency. The TiO 2 NPs were chemically functionalized by 3‐aminopropyltriethoxysilane (APTS) and 3‐methacryloxypropyltrimethoxysilane (MPTS), respectively. Scanning electron microscopy (SEM) studies revealed that APTS functionalized TiO 2 NPs tended to cluster in the polymer network instead of liquid crystal droplets, and MPTS functionalized TiO 2 NPs were independently and uniformly dispersed in the polymer network. Particularly, optical studies showed that the TiO 2 (MPTS)/PDLC composite film can effectively shield 95.9% UV light at on‐state, and 99.16% at off‐state. Furthermore, compared to traditional PDLC film (without TiO 2 NPs), the total response time of the TiO 2 (MPTS)/PDLC film is reduced from 60.4 to 13.4 ms, and the contrast ratio (CR) was increased by more than twofold from 35.6 to 97.26.