MOF-derived phosphide on nickel foam has been successfully synthesized (Mo–Ni₂P@NiO/NC/NF), and has been used as a bifunctional catalyst for both the HER at the cathode and the UOR at the anode for urea–water electrolysis. Mo–Ni₂P@NiO/NC/NF was used as the electrode to form a Mo–Ni₂P@NiO/NC/NF‖Mo–Ni₂P@NiO/NC/NF electrolysis cell, which showed a low voltage (1.496 V) for the UOR&HER at a current density of 10 mA cm⁻². Moreover, the electrocatalytic performance and morphology of Mo–Ni₂P@NiO/NC/NF are not changed in a long-term test, indicating that it has high activity and good stability. This study shows an efficient way to synthesize a promising bifunctional catalyst by developing MOF-derived phosphides on nickel foam.