Water electrolysis is relatively an environmentally friendly hydrogen production technology, but due to the slow transfer of four electrons in the anodic oxidation reaction, it needs a theoretical voltage of up to 1.23 V. Therefore, in this experiment, a series of transition metal oxides, ACo₂O₄ (A = Fe, Cu, Zn, Ni), was synthesized on Ni foam current collectors by a hydrothermal and calcination method, and the material was applied in urea electrolysis to produce hydrogen. What is noteworthy is that the CuCo₂O₄ electrode has a unique flower-like nanoneedle structure, and has a larger electrochemical active area, more reactive active sites, and a faster charge transfer rate. In 1.0 M KOH and 0.5 M urea solution, CuCo₂O₄ provides a potential of only 1.268 V at a current density of 10 mA cm⁻² during the urea oxidation reaction (UOR), while in 1.0 M KOH solution, with the same current density, the oxygen evolution reaction (OER) is required to provide a potential of 1.53 V, indicating that the UOR can effectively replace the OER. Density functional theory calculations show that the CuCo₂O₄ material exhibits Gibbs free energy of the hydrogen closest to zero, thus promoting the electrochemistry performance of the electrode. In a cell composed of CuCo₂O₄//CuCo₂O₄, the current density of 10 mA cm⁻² can be achieved by providing a potential of only 1.509 V. This work offers a novel scheme for reducing energy consumption of the OER and improving catalytic performance of the UOR.