Liquid crystalline aromatic polyesters (LCPs) are representative examples of thermotropic liquid crystalline polymers, whose structure-property relationships have been the subject of many researches. In this study, we synthesized organo-soluble liquid crystalline aromatic polyesters, and their composites with acetylene-terminated thermoset resins were prepared and characterized. Soluble LCPs were synthesized by employing 6-hydroxy-2-naphthoic acid, terephthalic acid, isophthalic acid, and 4-aminophenol as monomers via condensation polymerization based on transesterfication and transamidation. Acetylene-terminated thermoset resins were synthesized by the reaction of 4-ethynylaniline with terephthaloyl dichloride, isophthaloyl dichloride or 4,4′-biphenyldicarbonyl dichloride. We prepared the soluble LCP/thermoset composites by solution blending followed by thermal treatment. The thermal stability, thermal expansion coefficient, and dielectric properties of the composite were studied.