Development of efficient multifunctional electrocatalysts for hydrogen production from overall water splitting (OWS) and urea electrolysis (UE) is highly desired yet challenging. Herein, Ni-MoN nano-heterostructures encapsulated in NCNTs have been successfully fabricated on Cu foam (NMN@NC/CF), which exhibits excellent trifunctional catalytic activity toward the hydrogen evolution reaction (HER, eta 10, 1200 = 69, 265 mV), oxygen evolution reaction (OER, eta 10 = 191 mV) and urea oxidation reaction (UOR, E10, 500 = 1.316, 1.450 V), outperforming noble metal-based catalysts due to its unique structure and intrinsic catalytic capability. Furthermore, a two-electrode electrolyzer using NMN@NC/CF as both the cathode and anode needs a much lower voltage of 1.376 V for UE than the value of 1.521 V for OWS to reach 10 mA cm-2, and it can remain stable over 100 h during continuous UE operation at 500 mA cm-2, demonstrating great promise for simultaneous energy-saving hydrogen production and remediation of urea-containing wastewater.