Since urea is commonly present in domestic sewage and industrial wastewater, its use in hydrogen production by electrolysis can simultaneously help in water decontamination. To achieve this goal, the development of highly active and inexpensive urea electrolysis catalysts is necessary. This study deals with the preparation of multilayered nickel and copper phosphides/phosphates (NiCu-P/NF and NiCu-Pi/NF) supported on Ni foam (NF) and their application as new electrocatalyst types for the electrolysis of urea-containing wastewaters. In these materials, Cu atoms induce the formation of multilayer nanostructures and modulate electron distribution, allowing for the exposure of additional active sites and acceleration of the process kinetics. NiCu-P/NF is used as a cathode and NiCu-Pi/NF as an anode in an electrolysis cell and exhibits significant catalytic activity and stability in the urea oxidation reaction (UOR) and the hydrogen evolution reaction (HER). The NiCu-Pi/NF||NiCu-P/NF electrolysis cell, operating with an alkaline urea-containing aqueous electrolyte, achieves a current density of 10 mA cm- at a potential of 1.41 V, which is less than required by the RuO2||Pt/C cell utilizing commercial noble metal-based electrodes. The study provides a novel strategy for designing efficient catalysts to produce hydrogen by urea electrolysis.