This article describes the synthesis and swelling behavior of a superabsorbing hydrogel based on sodium alginate (NaAlg) and polyacrylonitrile (PAN). The physical mixture of NaAlg and PAN was hydrolyzed with a solution of NaOH to yield an alginate-poly(sodium acrylate-co-acrylamide) [Alg-poly(NaAA-co-AAm)] superabsorbent hydrogel. A proposed mechanism for hydrogel formation was suggested, and the structure of the product was established with Fourier transform infrared spectroscopy. The effects of reaction variables were systematically optimized to achieve a hydrogel with a swelling capacity as high as possible. Under the optimized conditions concluded, the maximum capacity of swelling in distilled water was 610 g/g. The absorbency of the synthesized hydrogels was also measured in various salt solutions. The swelling ratios decreased with an increase in the ionic strength of the salt solutions. In addition, the swelling capacity was determined in solutions with pHs ranging from 1 to 13. The Alg-poly(NaAA-co-AAm) hydrogel exhibited pH responsiveness, so a swelling-deswelling pulsatile behavior was recorded at pHs 2 and 8. This on-off switching behavior made the hydrogel as a good candidate for the controlled delivery of bioactive agents. Finally, the swelling kinetics of the hydrogels with various particle sizes were preliminarily investigated as well.