The study investigates the design and optimization of cobalt metaphosphate (Co₂P₄O₁₂) doped with vanadium (V) to enhance its electrocatalytic activity for water and urea splitting. The V-doped Co₂P₄O₁₂ (V-Co₂P₄O₁₂) is synthesized through a hydrothermal reaction and subsequent phosphorylation treatment. The morphology and electronic structure of V-Co₂P₄O₁₂ are optimized, leading to improved performance in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR). Theory calculations show that V doping optimizes the d-band center of Co atoms, enhances the binding strength of intermediates, and increases the density of states, thereby boosting the kinetics of catalytic reactions. Additionally, V doping promotes the formation of a thicker amorphous layer on the surface of Co₂P₄O₁₂, enhancing its alkaline corrosion resistance and stability. The multilevel nanostructures of V-Co₂P₄O₁₂ provide rich active sites for catalytic reactions. A two-electrode electrolyzer assembled with V-Co₂P₄O₁₂ delivers low voltages for overall water and urea splitting, demonstrating the promising potential of V-doping in regulating electrocatalytic activity for green electrocatalytic applications.The study investigates the design and optimization of cobalt metaphosphate (Co₂P₄O₁₂) doped with vanadium (V) to enhance its electrocatalytic activity for water and urea splitting. The V-doped Co₂P₄O₁₂ (V-Co₂P₄O₁₂) is synthesized through a hydrothermal reaction and subsequent phosphorylation treatment. The morphology and electronic structure of V-Co₂P₄O₁₂ are optimized, leading to improved performance in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR). Theory calculations show that V doping optimizes the d-band center of Co atoms, enhances the binding strength of intermediates, and increases the density of states, thereby boosting the kinetics of catalytic reactions. Additionally, V doping promotes the formation of a thicker amorphous layer on the surface of Co₂P₄O₁₂, enhancing its alkaline corrosion resistance and stability. The multilevel nanostructures of V-Co₂P₄O₁₂ provide rich active sites for catalytic reactions. A two-electrode electrolyzer assembled with V-Co₂P₄O₁₂ delivers low voltages for overall water and urea splitting, demonstrating the promising potential of V-doping in regulating electrocatalytic activity for green electrocatalytic applications.