Polymerization shrinkage and associated stresses are the main reasons for dental restorative failure. We developed a series of liquid crystal diacrylates and dimethacrylates which have markedly low polymerization shrinkage. In order to fully understand the effects of temperature-induced changes of molecular order on the photopolymerization process and performance properties of the generated polymers, the photopolymerization of a difunctional acrylate, 2-t-butyl-1,4-phenylene bis (4-(6-(acryloyloxy)hexyloxy)benzoate), which exists in the nematic liquid crystalline phase at room temperature, was investigated as a function of photopolymerization temperature over the nematic to isotropic range. Morphological studies suggested that a mesogenic phase was immediately formed in the polymer even if polymerization in thin films occurred above the nematic-to-isotropic (N→I) transition temperature of the monomer (Tn-i = 45.8 °C). Dynamic mechanical analysis of 2 × 2 mm cross-section bar samples polymerized at 60 °C showed reduced elastic moduli, increased glass transition temperature and formation of a more crosslinked network, in comparison to polymers formed at lower polymerization temperatures. Fractography analysis showed that polymers generated from the nematic liquid crystalline phase underwent a different fracture pattern in comparison to those generated from the isotropic phase. Volumetric shrinkage (2.2%) found in polymer polymerized from the nematic liquid crystalline phase at room temperature was substantially less than the 6.0% observed in polymer polymerized from an initial isotropic phase at 60 °C, indicating that an organized monomer can greatly contribute to reducing cure shrinkage.