AbstractA free-standing catalyst electrode for the urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) in a urea electrolysis cell was synthesized by electroplating a Ni–Fe alloy onto carbon felt, followed by phosphidation (P-NiFe@CF). The prepared P-NiFe@CF catalyst consisted of Ni5P4, NiP2, and FeP with 3D flower-like P-NiFe architecture on CF. P-NiFe@CF exhibited excellent electrocatalytic activity for the UOR (demanding only 1.39 V (vs. RHE) to achieve 200 mA cm−2), and for the HER with a low overpotential of 0.023 V (vs. RHE) at 10 mA cm−2, indicating its feasibility as a bifunctional catalyst electrode for urea electrolysis. A urea electrolysis cell with P-NiFe@CF as both the free-standing anode and cathode generated a current density of 10 mA cm−2 at a cell potential of 1.37 V (vs. RHE), which is considerably lower than that of water electrolysis, and also lower than previously reported values. The results indicate that the P-NiFe@CF catalyst electrodes can be used as free-standing bifunctional electrodes for urea electrolyzers.