A thermosetting matrix based on an unsaturated polyester resin was employed to realise a Polymer Dispersed Liquid Crystal (PDLC) system by a UV induced curing process. A molecular, morphological and thermo-optical characterisation of this system is presented. The chemical and structural properties were investigated by transmission FT-IR spectra in the near infrared frequency range and by dynamic-mechanical analysis. The results indicated that, upon curing, the matrix retains its intrinsic properties even for compositions very rich in the LC component (40 wt %). The morphology, investigated by optical and electron microscopy, showed phase separation before and after the curing process. Image analysis demonstrated that the cured materials had morphological features suitable to achieve interesting thermo-optical properties. In particular, the composition containing 40 wt % of LC exhibited the typical behaviour of a thermo-optical switch. Interesting optical bistability effects were also demonstrated for this particular composition.