Polymer dispersed liquid crystal (PDLC) materials were prepared by a polymerization induced phase separation (PIPS) process using UV radiation. The samples were obtained from the liquid crystalline component E7 and a blend of monofunctional (2-ethylhexyl acrylate) and difunctional (1,6-hexane diol diacrylate) monomers as precursors of the matrix. Polymerization energetics and thermodynamic properties of PDLC materials were studied by differential scanning calorimetry. Photopolymerization kinetics and phase behaviour of the PDLC are presented and discussed as a function of UV polymerization conditions (UV light intensity, UV time exposure and isothermal curing temperature).