Methoxybenzylidene n-butylaniline (MBBA) and ethoxybenzylidene n-butylaniline (EBBA) liquid crystal were synthesized. To investigate the applications of hydrophilic monomers and polymers on the field of liquid crystal composite film, 2-hydroxyethyl methacrylate (HEMA) and acrylic acid (Aa) were selected as monomers for the polymer matrix. To prepare the liquid crystal composite film, MBBA, EBBA, and commercial liquid crystals ZLI-2444, 2352, 2459, and BDH-E7 were mixed with HEMA, Aa, and photosensitive materials and then irradiated by UV light. The electro-optical behavior and the microstructure of the liquid crystal composite films were investigated by He-Ne laser and scanning electron microscopy, respectively. The effects of UV light irradiation and monomer ratio on the electro-optical behavior of liquid crystal composite films were investigated. The reproducibility and storage stability of the liquid crystal composite films were investigated.