A cholesteric, chiral, liquid-crystal polyester PTOBEE [C26H20O8](n), synthesized from the racemic mixture of their starting materials, showed an unexpected stereoselective separation of polymer units which incorporate a higher excess of one enantiomer at the expenses of the other when the polycondensation reaction products are decanted into a large excess of toluene. Am NMR diffusion study of PTOBEE obtained for a sample with 67% enantiomeric excess (ee) showed the formation of a complex by self-association of several polymer units with an unexpected higher tendency of the complex to be formed when the sample is further diluted. Cross saturation transferred NMR experiments showed the high stability of this complex and provided evidence of slow exchange equilibrium with the single polymer unit. The results suggest that both effects, the enantiomeric excess obtained after decantation in toluene, which was higher in the second fraction of the precipitate, and the high tendency of the complex formation in diluted samples of this polymer could be related. Polymer units incorporating a certain excess of one of the enantiomers could result in a privileged spatial geometry of the substituents which favors its self-aggregation, resulting in its precipitation during the synthetic process at two different kinetic rates.