The formation of stereocomplexes from the pair of enantiomorphs of the chiral polyamide poly(hexamethylene di-O-methyl tartaramide) was investigated for a variety of experimental conditions. DSC and X-ray diffraction data evidenced that efficiency in enantiomeric association is highly sensitive to the procedure used for preparing the complex. A comparative isothermal crystallization study revealed that the stereocomplex crystallized from the melt at a rate lower than the enantiomerically pure components. The radial growth of individual spherulites was also delayed in the crystallization of the complex. No evidence of stereocoupling was detected for other poly(alkylene di-O-methyl tartaramide)s with the alkylene unit length different from six. It was concluded that molecular interlocking of hydrogen bonds in the enantiomeric pair is highly selective in this family of polymers.