N.m.r. spectra (1H and 13C) of starch-derived polysaccharides contain several resolvable resonances due to minor structural features, which can be used for quantitative analysis. Thus, the degree of branching of amylopectins and native and degraded starches can be non-destructively determined and the reducing residues of degraded starches can be quantified. 13C-N.m.r. spectroscopy can also distinguish between glucose and the reducing residues of higher glucans.