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A method to establish the monomer composition of (bio) macromolecules has been developed. The method, to be called monomer mapping, involves the mass spectrometric determination of the molecular weight and a computer program. The program generates monomer compositions corresponding to the measured molecular weight. If more than one monomer composition for the polymer is generated by monomer mapping, a further limitation can be obtained from the determination of the number of exchangeable hydrogens. Monomer mapping can be used to determine the monomer compositions of individual components in mixtures without applying (chromatographic) separation techniques. This is a clear advantage over methods involving monomerization and consecutive determination of the relative amount of monomers. As a limitation, monomer mapping requires the elemental compositions of all monomer types possibly present in the polymer. The largest molecular weight resulting into one monomer composition depends on the number of monomer types considered. The method can be used as a supplement to amino acid analysis, generally resulting into the actual amina acid composition of peptides consisting of up to 25 amino acids. Monomer mapping was successfully applied to determine glycosyl compositions of fifty saponins.