Reversed-phase high-performance liquid chromatographic elution data for methionine-enkephalin-related glycoconjugates were analysed as a function of the identity and position of the sugar-peptide linkage. It was shown that binding to the column could be correlated with the degree of sugar moiety protection. Replacement of either the phenylalanine or methionine residue in the peptide backbone of the glycoconjugates with its D-enantiomer leads to a considerably stronger retention on a reversed-phase column. The dependence of retention times on the methanol concentration in the mobile phase suggested that, under the conditions studied, there are different retention mechanisms for glycopeptides containing unprotected sugar moieties in the molecule.