In this study, one pot synthesis of nickel nanoparticles immobilized on reduced graphene oxide-branched polyethyleneimine (NiNPs@rGO-bPEI) aerogel is reported. To produce graphene-based supramolecular hydrogel, bPEI with a high density of amine groups was used as a cross-linking agent. The simultaneous co-reduction of GO and nickel ions was carried out using sodium borohydride (NaBH4). The catalytic activity of the NiNPs@rGO-bPEI aerogel was investigated for hydrogen generation from the hydrolysis of NaBH4 at room temperature. The effect of various amounts of bPEI as the linking agent on the structure of the aerogel product was investigated. Moreover, the influence of various amounts of nickel loading on the catalytic activity of NiNPs@rGO-bPEI was also studied. The ease of synthesis (only at one step), low cost, being environmentally benign, existence of nitrogen and nickel to have interaction with molecular hydrogen, and also the large surface area are the key features of the synthesized catalyst that makes it suitable for industrial applications. [GRAPHICS] .