<p>This study investigated the synthesis and characterization of the cerium oxide (CeO₂) and nickel (Ni) doped carbon nanofibers (CNFs) catalyst and evaluated its electrochemical performance for urea oxidation. The successful doping of CNF with CeO₂ and Ni is confirmed through electron microscopy and X-Ray diffraction analyses. The catalyst’s efficiency is examined using cyclic voltammetry (CV) tests, with results demonstrating a low onset potential and high current densities (+ 30&#xa0;mA/cm²), thereby validating its suitability for green hydrogen production. Different parameters have been manipulated in the CV tests: the calcination temperature while preparing CeO₂/Ni-doped CNF (700 to 1000&#xa0;°C), the % cerium acetate (Ce(Ac)₃) in the prepared CNF (0–15%), the urea concentration (0 to 3&#xa0;M), the scan rate (20–100 mV/s), and the reaction temperature (30–60&#xa0;°C). The electrochemical performance of CeO₂/Ni-doped CNFs was systematically optimized, with the best results achieved under specific conditions: a calcination temperature of 850&#xa0;°C, 5 wt% Ce(Ac)₃ in the CNF precursor, and a catalyst loading of 70&#xa0;µg/cm². Electrochemical testing revealed that a scan rate of 100 mV/s, a supporting electrolyte concentration of 5&#xa0;M KOH, and a urea concentration of 2&#xa0;M provided the highest current densities and most stable performance. These conditions collectively enhanced the catalytic activity and stability of the material, making it a promising candidate for urea electrooxidation applications. In addition, the change of transient current density <i>I</i> with time t by changing the potential stepwise V(t) showed a stable performance of urea oxidation over the active sites at different applied potential from 0.2 to 1&#xa0;V vs. RHE. This research contributes to the evolution of cost-effective technologies for hydrogen storage and transportation, illustrating the significance of catalyst design and optimization. It explains a step in the hydrogen storage and reuse cycle.</p>