The importance of residue sequence and duplex and triplex structures as basis for establishing molecular understanding of the structure–function relationships within glycopolymers is highlighted. The copolysaccharide alginate is the selected example for elucidating effects of residue sequence on functional properties like ionotropic gelation. Xanthan and comblike branched β-d-glucans are used as examples of impact of duplex and triplex organization on global conformation and functional properties. Combined with further examples within self-interactions of mucins possessing different saccharide decorations, polyelectrolyte complexation and multilayer formation, the examples indicate that a molecular understanding of various properties related to impact of residue sequences, duplex, and triplex organization can be established. Strategies similar to those included in the highlighted examples, also combined with novel tools, for example single-molecule approaches, interrogated by combination of experimental and theoretical/numerical approaches, and investigated closer to the native biological state, are expected to further advance the field. © 2013 Wiley Periodicals, Inc. Biopolymers 99: 757–771, 2013.