Abstract Starches from ten yam ( Dioscorea ) species were compared with those of maize, wheat, potato and cassava, and characterized by high‐performance size‐exclusion chromatography coupled with multiangle laser light scattering. Treatment with 95% (v/v) dimethylsulphoxide and microwave heating in a high‐pressure vessel led to complete dissolution of the starch samples. For yam starches, M̄ w were between 1.88 × 10 8 and 3.27 × 10 8 g mol −1 and R̄ G were between 258 and 396 nm. The hydrodynamic coefficients of amylopectins were between 0.36 and 0.44, indicating that those of maizes and esculenta 5 and dumetorum yam species had particularly highly branched structures. Multidimensional analysis of the macromolecular characteristics of yam starches indicated three classes: dumetorum cultivar ( Dioscorea dumetorum ), esculenta 5 cultivar ( Dioscorea esculenta ) and the other eight yam starches, including cultivars of Dioscorea alata and Dioscorea cayenensis‐rotundata species. Some yam starches were also leached at 90 °C. The macromolecular characteristics of the leached fractions confirmed the previous typology. Copyright © 2003 Society of Chemical Industry