Polymer dispersed liquid crystal (PDLC) films’ morphologies and electro-optical properties have been mostly investigated on the method of polymerization, rate of reaction, the relative amount, characteristic, and temperature of the LC/monomer mixtures; in chorus with the molecular associations existing among the LC, monomer molecules and with the glass. In this effort the molecular associations of polymer matrix having hydrophilic and hydrophobic characteristics are considered with the LC. Here the hydrophilic/hydrophobic interactions of material are deduced equally accountable for change in the morphology, electro-optical properties and phase separation of PDLC films. For such investigations the spectroscopic techniques such as Fourier transform infrared (FTIR) spectroscopy, polarized optical microscopy (POM) and phase transition temperatures have been implemented which appreciably elucidate the subsequent studies.