The weight average molar mass (Mw) and root mean square radii of starches from waxy maize (Amioca), waxy rice flour, cassava, Hylon V, Hylon VII, and potato amylose were determined by size‐exclusion chromatography (SEC) and multiple‐angle laser light scattering (MALLS). Dimethylsulfoxide (DMSO) containing 50 mM LiBr was used to dissolve the starches and also served as the mobile phase. SEC with large particle size polystyrene divinylbenzene packing materials and MALLS instrumentation were evaluated for the ability to separate and determine molar mass (MM) of starch polymers, respectively. The determination of Mw by MALLS is necessary because the Mw of many cereal starches exceeds the available molecular standards by one or two orders of magnitude. The Mw depends on the method of calculation. The Mw (Berry method) of starch from waxy corn was 2.27 × 108 Da, waxy rice 8.9 × 107 Da, cassava 5.7 × 107 Da, Hylon V 2.7 × 107 Da, Hylon VII 4.8 × 106 Da, and potato amylose 1.9 × 105 Da. Recovery dropped dramatically for molecules with root mean square radii >200 nm.