In order to solve the environmental degradation issues induced by the overuse of fossil energy and indiscriminate discharge of urea-rich wastewater, it is imperative to design high-performance electrocatalysts with dual functions for both hydrogen evolution reaction (HER) and urea oxidation reaction (UOR) applied in water electrolysis devices containing urea. In this text, we demonstrate an interfacial engineering to prepare a heterostructure of porous Ni3S2 nanospheres decorated CoP nanoplates on NF scaffold (NF/CoP@Ni3S2). It exhibits the eminent catalytic competence towards HER (-68.9 mV at 10 mA cm−2) and UOR (1.379 V at 100 mA cm−2). Moreover, whether for HER or UOR, its performance degradation is almost negligible after working for 27 h at 50 mA cm−2. Finally, the constructed (−)NF/CoP@Ni3S2||Ni3S2@CoP/NF(+) device just needs 1.574 V to afford a current density of 100 mA cm−2 with an outstanding durability (only 4.2 % of the voltage rise is observed after electrolyzing for 27 h). This work not only provides a new possibility to fabricate metal phosphide-sulfide assemblies with advanced performance, but also offers an attractive way to mitigate water pollution in an eco-friendly way and provide an alternative energy source.