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The current work aimed to fabricate polymer dispersed liquid crystal (PDLC) films using heterocyclic acrylate monomers containing oxygen atoms. The incorporation of oxygen heterocycles into the host polymer matrix significantly improved the electro-optical properties of PDLC films. Particularly, the high contrast ratio 330.0 was realized for the monomer Trimethylolpropane formal acrylate (TFA). Further, the excellent electro-optical properties, including low driving voltage (10.0 V), moderately high contrast ratio (64.0) and short response time (<8.0 ms) were obtained when the liquid crystals/polymer composite film thickness decreased from 20 μm to 8 μm. This work has provided a novel materials system to promote the application of PDLC films in the thin-layer liquid crystal display.