Crosslinked poly(acrylamide) (p(AAm)) as neutral hydrogel is synthesized via photo polymerization technique, and the amide groups within p(AAm) matrices are converted to strongly ionizable carboxylic acids groups via facile modification route by simple treatment of NaOH to obtained NaOH-p(AAm) hydrogels. Because of the highly ionizable nature of carboxylate groups within mod-p(AAm), the swelling and metal ion absorbing capacities are increased tremendously, almost 40 and 7.5 folds, respectively. The Co(II) and Ni(II) metal ions are loaded into NaOH-p(AAm) hydrogels, and are treated with NaBH4 to form corresponding metal nanoparticles in situ within mod-p(AAm) matrices, and used in H2 generation production from hydrolysis of NaBH4. Various parameters such as functionality of polymeric matrices, the kinds and the amount of metal nanoparticles, and the temperature effecting the H2 generation are investigated. Comparable low Ea with the similar researches in the literature, Ea = 20.07 ± 0.05 kJ mol−1 is obtained in NaBH4 hydrolysis catalyzed by NaOH-p(AAM)-Co composite system. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41106.