We synthesized optically active compounds having a menthyl group as a chiral additive that induces a cholesteric phase in a nematic liquid crystal (NLC) and a homeotropic orientation in a smectic A* phase (SmA*LC). 2,2',5',2 ''-Ter(3,4-ethylenedioxy-thiophene) (terEDOT) can be electropolymerized in LC electrolyte solution containing the optically active compound. Polymerization in a cholesteric liquid crystal (CLC) electrolyte solution produced by the chiral inducer yielded poly(terEDOT) showing chiral aggregation with one-handed helices. The resultant poly(terEDOT)s obtained in the CLC electrolyte solution displayed complementary mirror-image bisignate Cotton effect. Furthermore, polymerization in SmA*LC electrolyte solution in a homeotropic orientation afforded a poly(terEDOT) with vertically oriented morphology.