Bimetal materials derived from transition metals can be good catalyst candidates towards some specific reactions. When loaded on graphene (GP), these catalysts exhibit remarkable performance in the hydrolysis of sodium borohydride. To obtain such catalysts easily and ef-ficiently, a simple thermal reduction strategy was used in this study, and NixCo10?x series bimetal catalysts were prepared. Among all the cata-lysts, Ni1Co9 exhibited the best catalytic performance. The turnover frequency (TOF) related to the total number of atoms within the bimetallic nanoparticles reached 603.82 mL·mmol?1·min?1 at 303 K. Furthermore, graphene was introduced as a supporting frame. The Ni1Co9@Graphene (Ni1Co9@GP) had a large surface area and high TOF, 25534 mL·mmol?1·min?1, at 303 K. The Ni1Co9@GP exhibited effi-cient catalytic properties for H2 generation in alkaline solution because of its high specific surface area. Moreover, the high kinetic isotope ef-fect observed in the kinetic studies suggests that using D2O led to the oxidative addition of an O–H bond of water in the rate-determining step.