Liquid-crystalline thermosets (LCT) are a new class of materials which combine typical properties of LC polymers with those of conventional thermosets. This article reports on the development of a lyotropic LC thermoset (LLCT) in which the solvent is a vinyl monomer. Such an LLCT is expected to have several advantages compared to conventional unsaturated polyester resins. The synthesis and characterization of a variety of novel substituted para-linked aromatic polyesters and copolyesters containing unsaturated fumaroyl units is presented. The thermal and liquid crystal properties were investigated. It is demonstrated that it is possible to prepare a lyotropic LC solution in styrene. These lyotropic solutions are capable of thermal crosslinking by the addition of a free-radical initiator.