The present invention features a method for the formation of superporous hydrogels using an ion-equilibration technique. Anionic polysaccharides are included in the hydrogel reaction mixture and cations are introduced either during or after hydrogel formation. Properties of the resulting hydrogel can be subsequently adjusted by treating the cation-complexed gel with a different cation or cation mixture under equilibrating conditions. It has been found that by properly adjusting the cations and the sequence in which they are used in the equilibration process, superporous hydrogels can be formed that are highly absorbent while maintaining favorable structural properties, including strength, ruggedness, and resiliency. It has also been found that applying appropriate dehydration conditions to them after their formation can further stabilize the superporous hydrogels formed by the method of the invention.