Starch graft superabsorbents were prepared by graft copolymerization either with polyacrylonitrile (PAN) and saponification of the resulting copolymer or with trimethyl–aminoethylacrylate chloride (CMA) and methylene bisacrylamide as crosslinking agent. The influence of several structural parameters on the swelling properties of these absorbents have been studied: crosslink density, ionic content, and composition of the starch. As expected, the absorbency decreases with an increase of the crosslink density. It increases with the ionic content of the graft copolymer up to a maximum, an excess of charges leading to a swelling decrease. The PAN branch length depends on the origin of the starch. High molar weight PAN was grafted onto waxy corn, a starch with high amylopectin content. The swelling increases with increasing molar weight of PAN up to 5 × 105. In saline solution the absorbency of both ionic gels decreases significantly. However, in the presence of multivalent ions their behavior is different. For cationic absorbents the swelling depends on the ionic strength but not on the ion valency. On the other hand, anionic absorbents are significantly affected by multivalent cations.