This article describes the synthesis and characterization of new liquid crystalline thermosets having a twin structure. Nematic epoxy-terminated monomers based on a phenyl benzoate twin mesogen connected by an alkylene spacer were synthesized for these studies. In addition, an epoxy-terminated monomer based on a 1,4-bis(benzoyloxy)phenylene mesogen was synthesized to determine the effect of the position of the mesogen on the final network structure. The diepoxy monomer made with phenyl benzoate twin mesogens connected with an alkylene spacer formed a smectic-like network when cured with diamines. This smectic organization appeared even though the diepoxy monomer itself showed only a nematic mesophase over a narrow temperature range. The presence of crosslinks at both ends of the mesogens helped to retain a uniform spacing between crosslinking sites during the curing reaction, and aided formation of the smectic layer arrangement. The epoxy monomer possessing a 1,4-bis(benzoyloxy)phenylene mesogen and two epoxidized alkylene end groups on both sides of the mesogen formed a stable nematic mesophase. However, in contrast to the twin epoxies, the latter epoxy when reacted with diamines tended to produce a nematiclike network which was retained as the crosslinking reaction proceeded.