Glycerol is often added to starches to plasticize the product, but the presence of glycerol may also affect the water content of the samples. To evaluate the effect of glycerol on the sorption properties of starches, waxy maize, rice, and wheat starch were thermomechanically extruded in the presence of glycerol. Sorption isotherms of these extruded samples were ascertained using dynamic vapor sorption (DVS). BET and GAB modeling showed a monolayer (m o) significantly higher for waxy maize than for rice and wheat. Glycerol inclusion changed the model values, indicating reduction in sorption energy at the monolayer and restructuring of the multilayer. An interaction factor (ξ) based on weight fraction models was calculated. Differences in ξ were obtained when glycerol was added, varying from ∼0.9 for 5% glycerol to ∼0.8 for 20% glycerol, supporting the hypothesis of interactions between starch and this polyol.