NiCo2O4 nanowire arrays grown on Ni foam (NiCo2O4/NF) are synthesized by a simple template-free hydrothermal route followed by a thermal treatment in the air at 400 °C. The as-prepared Ni foam substrate exhibits homogeneous and porous nanowire arrays, which providing a number of active sites and electronic transmission channels for urea electrooxidation. The electroactivity of NiCo2O4/NF electrode toward the oxidation of urea in alkaline solution is evaluated using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) measurements. Results show that the as-obtained electrode delivers an outstanding electrocatalytic activity and stability for urea electrooxidation. The NiCo2O4/NF electrode delivers a low open potential at 0.19 V versus Ag/AgCl with a corresponding current density of 570 mA cm−2 in 5 mol L−1 KOH and 0.33 mol L−1 urea electrolytes. Meanwhile, detailed investigation is made for the electrocatalytic oxidation of urea by varying several reaction parameters, such as scan rate, urea and KOH concentrations. Benefiting from the unique structure and synergistic effects of Ni and Co, the NiCo2O4/NF electrode exhibit superior electrocatalyst activity and is considered to be a promising candidate catalysis material for direct urea fuel cell.