Urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) are the key processes for implementing urinated water electrolysis and hydrogen green production, respectively. This contribution investigates the modification of commercial nickel foam (NF) with a nickel phosphate (NiPO/NF) heterostructure layer via anodizing in phosphate solution at various potentials (5, 10 and 15 V) as a simple and efficient route to boost the urea-assisted water electrolysis and hydrogen production in alkaline medium. The morphology and composition physicochemical characterisation of the phosphate layer exhibit aggregates of crystalline nanoparticles with interstitial mesoporous and macroporous networks with a mole composition ratio of 9.42: 1.0: 8.14 for Ni: P: O respectively. The electrochemical measurements revealed the NiPO/NF anodized at 10 V exhibits a superior electroactive surface area of 255 cm2, a substantially higher urea oxidation current compared to pristine NF, achieving 20 and 500 mA/cm2 at 1.35 and 1.6 V vs. RHE respectively and retained 100 % of activity during the urea electrolysis for more than 3 h. The electrochemical impedance analysis confirmed the alkaline urea oxidation reaction proceeded via indirect (EC) and direct mechanism and the CO2 intermediates adsorption–desorption became the predominant reaction at more positive potential. The NiPO/NF anode employed in an H-shape can deliver up to ±400 mA/cm2 for UOR/HER at a bias potential of 1.85 V and 8-fold (2.0 mmol/min) much higher hydrogen production rate compared to the pristine NF anode (0.25 mmol/min). Combining commercial nickel foam modification via anodizing and alkaline urea electrolysis at ambient conditions offers a unique and innovative solution for both large-scale hydrogen green production as well as remedy of the urinated wastewater for a more sustainable future.