We have synthesized a series of mono-substituted thiophene derivatives with phenylalkyl and liquid crystalline groups and polymerized them through a chemical oxidative polymerization and a dehalogenative polycondensation, respectively. Poly(phenylalkyl-substituted thiophene)s were found to have highly stereoregular configurations composed of head to tail linkages. The dehalogenative polycondensation of the 2,5-dibrominated thiophene monomer with the liquid crystalline group at the 3-position of thiophene ring showed a monotropic nematic phase with a schlieren and droplet texture in polarizing optical micrograph. All polymers were characterized in terms of chemical and spectroscopic properties as well as electrical conductivities before and after iodine doping.