One-dimensional porous Co₃O₄ nanowires are successfully prepared by thermal decomposition of a coordination polymer, using nitrilotriacetic acid (NA) as a chelating agent via a solvothermal method. The Co₃O₄ nanowires with porous structure comprise numerous nanoparticles and maintain the nanowire structure of Co–NA precursors. When evaluated for supercapacitor electrode materials, Co₃O₄ nanowires exhibit superior electrochemical properties. A high specific capacitance of 2815.7 F g⁻¹ at 1 A g⁻¹ can be observed with a desirable rate specific capacitance of 765 F g⁻¹ at 20 A g⁻¹. Fortunately, the capacitive behaviors of the obtained porous Co₃O₄ nanowire electrodes are superior among reported cobalt oxides, and the excellent coulombic efficiency (about 100%) and good cycling property demonstrate high electrochemical stability and tremendous potential for high performance supercapacitors.