The synthesis and cationic polymerization of (2S, 3S)-(+)-2-chloro-3-methylpentyl 4’-(2-vinyloxyethyloxy)biphenyl-4-carboxylate (15-2) and (2S, 3S)-(+)-2-chloro-3-methylpentyl 4’-(3-vinyloxypropyloxy)biphenyl-4-carboxylate (15-3) are described. The mesomorphic behavior of the resulting polymers is discussed as a function of the molecular weight and spacer length. Based on the second and subsequent heating and cooling scans, poly(15-2)s exhibit an enantiotropic S(X) (unidentified smectic) phase. Poly(15-2) with DP=4 is only crystalline. Poly(15-3)s show an enantiotropic cholesteric phase and an inverse monotropic S(X) phase.