Polyelectrolite hydrogels are crosslinked polymers which display high sorption capacity in water and water solutions. They are widely used in the marked of personal hygiene products, as well as in other biomedical and industrial applications. In the most industrial application they are not biodegradable and prepared starting from acrylamide. In this work, the chemical-physical analysis of a novel class of natural polymers-based microporous superabsorbent hydrogels has been presented. The main focus is the definition of the relationship between material's chemical-physical structure and its equilibrium sorption properties. The effect of the variation of the degree of crosslinking, the polyelectrolyte nature of the backbone and the hydrogel microporosity on its swelling properties has been analysed, and a good agreement with the theoretical statements has been displayed. The effect of the ionic strength and the pH of the external solution in contact with the hydrogel on its equilibrium sorption properties has also been assessed, and an high sensitivity to these variations was detected for all the tested chemical compositions and physical structures. This work have to be considered part of the efforts towards the reduction of the environmental impact of the large scale consumption industrial polymer based products. (c) 2005 Elsevier Ltd. All rights reserved.