(R)-2-Chloro-4-methylpentyl 4’-[[8-(vinyloxy)octyl]oxy]biphenyl-4-carboxylate ((R)-8) (R > 95%) and (S)-2-chloro-4-methylpentyl 4’-[[8-(vinyloxy)octyl]oxy]biphenyl-4-carboxylate ((S)-8)(S > 95%) enantiomers and their corresponding homopolymers and copolymers with well-defined molecular weight and narrow molecular weight distribution were synthesized and characterized. The phase behavior of the two enantiomeric polymers can be compared only by superimposing the dependence of their transition temperatures as a function of molecular weight. 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 monotropic S(A) and S(C)* phases and a crystalline phase, while the corresponding polymers exhibit enantiotropic S(A), S(C)*, and S(X) (unidentified smectic) mesophases. Phase diagrams were investigated in detail in binary mixtures of (R)-8 with (S)-8, poly[(R)-8] with poly[(S)-8] and in 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. This is in contrast to the crystalline phase of the monomers whose phase diagram displays an eutectic composition. The S(A)-I transition of the binary mixture of (R)-8 with (S)-8 is within 0.4-degrees-C higher 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 SA phase. Heterochiral recognition was not detected in the S(C)* phase of any of the enantiomeric pairs investigated. In the polymer mixtures, the chiral recognition observed in the S(A) phase of the monomer mixtures is enhanced with increasing the degree of polymerization (DP) up to about 10 to reach a positive deviation of 1.3-degrees-C from the theoretical ideal value. However, polymer mixtures with DP higher than 14 showed smaller positive deviations of their S(A)-I transitions than those of the corresponding monomer mixtures. These results indicate the existence of an optimum molecular weight for the manifestation of heterochiral recognition. In the copolymer system, no clear trend was observed with respect to any phase.