The synthesis and characterization of (R)-2-fluoro-4-methylpenbtyl4’-((8-(vinyloxy)octyl)oxy)-biphenyl-4-carboxylate((R)-8(R>95%) and (S)-2-fluoro-4-methylpentyl 4’-((8-(vinyloxy)octyl)oxy)biphenyl-4-carboxylate ((S)-8) (S > 95%) enantiomers and of their corresponding homopolymers and copolymers with well-defined molecular weights and narrow molecular weight distributions are presented. The phase behaviors of (R)-8 and poly[(R)-8] are identical to those of (S)-8 and poly[(S)-8], respectively. Both monomers display enantiotropic S(A) and S(C)* phases, a monotropic S(X) (unidentified smectic) phase, and a crystalline phase, while the corresponding polymers exhibit only enantiotropic S(C)* and S(X) mesophases. Phase diagrams were investigated in detail for binary mixtures of (R)-8 with (S)-8 and poly[(R)-8] with poly[(S)-8] and for binary copolymers of (R)-8 with (S)-8 as a function of the composition of the two enantiomeric structural units. In all these systems the two enantiomeric structural units derived from the two monomers are miscible within all their mesophases and over the entire range of composition. The S(A)-I and the K-S(C)* transition temperatures of the binary mixture of (R)-8 with (S)-8 are 0.4 and 3.8 deg higher, respectively, in the 50/50 mixture than the theoretical value expected for an ideal solution, demonstrating the presence of heterochiral molecular recognition between the two enantiomers in their S(A) and crystalline phases. Heterochiral recognition in the S(C)* phase, which was not detected in the monomer mixtures, was observed in the polymer mixtures. The polymer mixtures with the lowest degree of polymerization (DP = 5) showed the largest positive deviation (ca. 0.5 deg) of the S(C)*-I transition temperature from the ideal value. With increasing molecular weight of the polymers from the mixture, the positive deviation decreased and the chiral recognition was almost canceled at DP = 15. In the copolymer system, chiral recognition was observed in both the S(C)* and S(X) phases. The positive deviation of the S(C)*-I transition temperature from the ideal value was 1.0 deg, and this value was much larger than that of the polymer mixtures with the same molecular weight (0.1-0.2 deg). Chiral recognition in the S(X) phase of copolymers is unexpected since this effect was not present in the polymer mixtures. Thus, for the first time on enhancement of chiral molecular recognition was observed in copolymers.