Birefringence analysis was used to measure thermal transitions in liquid crystal diacrylate monomers and their corresponding polymers. In this technique, linearly polarized light was used to probe the sample as the temperature increased via a linear ramp. Various phase transitions were observed in the liquid crystalline monomers. In addition, the monomers were isothermally photopolymerized in the liquid crystalline state and the resulting polymer networks retained their liquid crystalline order. Glass-to-rubber transitions as well as indications of further thermal polymerization and stress relaxation were detected. Results from birefringence experiments were compared to those of more traditional thermal analysis techniques including DSC and TMA.