Hydrogen gas has been considered an eco-friendly energy source with a high energy content, making it a suitable energy carrier for several industries. A cerium-organic framework, denoted as CeOF, was synthesized by reacting cerium with a tricarboxylic organic linker using a solvothermal method. The material's characteristics were analyzed using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and Fourier transforms infrared spectroscopy (FT-IR) to confirm its crystallinity, phase purity, elemental composition, chemical bonding, morphology, and thermal stability. CeOF catalysized the release of hydrogen from solid hydrogen storage materials, e.g., sodium borohydride (NaBH4) by the reaction with water via hydrolysis. An examination was carried out to analyze the influence of catalyst loading, NaBH4 weight (0.2–3 wt.%), and reaction temperature. The CeOF catalyst showed a significant hydrogen generation rate (HGR) of 1800 mLH2·gcat-1·min−1, with an activation energy of 58.8 kJ·mol−1. It showed good catalytic recyclability enabling continuous hydrogen production for four cycles without any significant decrease in the material’s performance.