New homologous FLCs (I-11-n [n= 1-41) derived from optically active 5-alkyl-6-valerolactones were synthesized. Their mesomorphic properties were systematically investigated with respect to their molecular structures, which were different in terms of the length of an alkyl group attached to a chiral centre and the direction of phenylpyrimidyl group. For compounds type I-n, with pyrimidyl group conjugated to the terminal position carrying chiral 5-fluoro-alkyloxy tail, elongation of the attached alkyl groups enhanced the stability of the chiral smectic C phase, while the other type, with pyrimidyl group conjugated to the terminal position carrying achiral alkyloxy tail, showed no remarkable alteration in the stability of the phase. Short optical response time ( 2 2~s . 80°C[Tc-T=10K]) was found for the FLC 11-3 that has almost the same magnitude of spontaneous polarization (25nC~m-~, 80°C[Tc-T= IOK]) with that of 11-4.