Abstract: 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 efficiently, a simple thermal reduction strategy was used in this study, and Ni_xCo_10−x series bimetal catalysts were prepared. Among all the catalysts, 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 efficient catalytic properties for H₂ generation in alkaline solution because of its high specific surface area. Moreover, the high kinetic isotope effect 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.