An increase in the rate of polymerization of a cholesteryl-modified methacrylate functionality in a smectic liquid crystalline phase, compared to an isotropic medium, was attributed to a substantial decrease in the termination rate. Distinct changes in the medium composition and order when polymerization was initiated with the monomer initially in an isotropic phase resulted in rate acceleration processes. The rate acceleration process was again attributed to a decrease in the rate of termination. Polymerization of the methacrylate monomer at lower temperatures resulted in incomplete conversion due to a glassy matrix effect. Similar polymerization rate behavior was demonstrated for two other liquid crystalline monomers of similar structure.