This paper presents hydrogen generation measurements from the hydrolysis of NaBH4 aqueous solutions catalyzed by Co doping on single, bimetallic and trimetallic oxide supports (Co/CuO, Co/NiO, Co/Al2O3, Co/NiO–Al2O3, Co/CuO–Al2O3, and Co/CuO–NiO–Al2O3). Support materials are synthesized by the co-precipitation method. Then, Co is doped into support materials by the impregnation method. It is found that Co/CuO–NiO–Al2O3 catalyst exhibited high reaction activity with a maximum hydrogen generation rate (HGR) of 2067.2 ml min−1 gcat−1 at 25 °C. The effect of temperature of the solution, Co amount, and recyclability of the catalyst on hydrogen generation with Co/CuO–NiO–Al2O3 catalyst is investigated in detail. In addition, the highest HGR for Co/CuO–NiO–Al2O3 catalyst is obtained at 55 °C as 6460.0 ml min−1 gcat−1. The activation energy is calculated to be 31.59 kJ mol−1 using Co/CuO–NiO–Al2O3 catalyst. Co/CuO–NiO–Al2O3 catalyst exhibits zero-order reaction kinetics concerning NaBH4 concentration. In addition, the Co/CuO–NiO–Al2O3 catalyst provided high reusability after 5 cycles.