An advance of highly efficient nanostructured electrocatalysts based on non-noble metals for water electrolysis and urea oxidation reaction (UOR) are of great significance for urea-enriched wastewater remediation and producing hydrogen. Herein, we report VxNi1-xO catalysts supported on three-dimensional Ni-foam scaffold for catalytic water and urea electrolysis. VxNi1-xO catalysts show rapid water and urea electrolysis due to enhanced electrochemical surface area (ECSA). Most important of all, the urea oxidation reaction has a lower potential of 1.418V vs RHE as compared to oxygen evolution reaction (1.684 V vs RHE) system to generate 100 mA/cm2. Additionally, a two-electrode cell for bi-functional water electrolysis generates 100 mA/cm2 at a potential of 2.10 V at 20 °C and just 1.86 V at 60 °C temperature due to regulated the adsorption/desorption of intermediates species, enhanced charge and mass transport, and easier desorption of oxygen molecules from the anode. The stability of VxNi1-xO catalyst was measured at 1000 mA/cm2 current density for up to 17 h.