Polymer dispersed liquid crystal (PDLC) films are fabricated with various compositions of E7 liquid crystal (LC), 2-Hydroxy ethyl methacrylate (HEMA), Methyl methacrylate (MMA), n-butyl methacrylate (nBMA), Ethyl methacrylate (EMA), Tetraethylene glycol diacrylate (TEGDA), and Benzoin. The results show that the refractive index of the PDLC films is insensitive to the monomer side groups. The effects of different monomers addition on the microstructure, the corresponding polymer matrix motion and electro-optical properties of the PDLC samples are examined using Dynamic Mechanical Analyzers (DMA) and UV-Vis spectroscopy, respectively. The experimental results reveal that the addition of HEMA and TEGDA yields a considerable improvement in the electro-optical properties and the contrast ratio. Overall, the results show that a PDLC comprising 40wt% E7 liquid crystals, 50mol% TeGDA and 50mol% HEMA has both a high contrast ratio (12.75:1) and a low driving voltage (16 V), and is therefore a suitable candidate for smart window and a wide variety of intelligent photoelectric applications.