Urea electrolysis is a promising energy-efficient hydrogen production process with environmental benefits, but the lack of efficient and sustainable ampere-level current density electrocatalysts fabricated through simple methods is a major challenge for commercialization. Herein, we present an efficient and stable heterostructure electrocatalyst for full urea and water electrolysis in a convenient and time-efficient preparation manner. Overall, superhydrophilic/superaerophobic CoMn/CuNiP/NF exhibits exceptional performance for the hydrogen evolution reaction (HER) (−33.8, −184.4, and −234.8 mV at −10, −500, and −1000 mA cm–2, respectively), urea electro-oxidation reaction (UOR) [1.28, 1.43, and 1.51 V (vs RHE) at 10, 500, and 1000 mA cm–2, respectively], and oxygen evolution reaction (OER) [1.45, 1.67, and 1.74 V (vs RHE) at 10, 500, and 1000 mA cm–2, respectively]. Moreover, the superaerophobic CoMn/CuNiP/NF demonstrates promising potential in full urea (1.33, 1.57, and 1.60 V at 10, 500, and 1000 mA cm–2, respectively) and water (1.46 V, 1.78, and 1.86 at 10, 500, and 1000 mA cm–2, respectively) electrolysis. Based on X-ray photoelectron spectroscopy results, it was determined that the surface of the CoMn/CuNiP electrode was rich in redox pairs such as Ni2+/Ni3+, Cu+/Cu2+, Co2+/Co3+, and Mn2+/Mn3+, which are crucial for the formation of active sites for the OER and UOR, such as NiOOH, MnOOH, and CoOOH, thereby enhancing the catalytic activity. Besides, the in situ assembled CoMn/CuNiP/NF displayed highly stable performance for HER, OER, and UOR with high Faradaic efficiency for over 500 h. This research offers a simple and efficient method for manufacturing a high-efficiency and stable trifunctional electrocatalyst capable of delivering ampere-level current density in urea-assisted hydrogen production. Our density functional theory calculations reveal the potential of CoMn/CuNiP as an effective catalyst, enhancing the electronic properties and catalytic performance. The near-zero Gibbs free-energy change for HER underscores its promise, while reduced CO2 desorption energies and charge redistribution support efficient UOR. These findings signify CoMn/CuNiP’s potential for electrochemical applications.

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