Porous carbon materials are widely used as adsorbent and electrode materials due to its high specific surface area and low cost, while vanadium nitride, with excellent conductivity, good environmental stability and high reaction selectivity has been widely used as electrode material. Herein, the interconnected porous carbon derived from the precursor polystyrene is used as adsorbent to adsorb vanadate ions, and the carbon/vanadium complex is further heat-treated under ammonia atmosphere to convert it to vanadium nitride. The final obtained hybrid composite of interconnected porous carbon@vanadium nitride consists of vanadium nitride nanoparticles on the surface of porous carbon. The electrode material prepared with the hybrid composite exhibits a high specific capacitance of 260 F g−1 at 0.5 A g−1 and a good rate capability with capacitance retention of 74.6%. Furthermore, the hybrid supercapacitor assembled with Ni (OH)2 exhibits a high specific capacitance of 129 F g−1 at the current density of 1 A g−1. Remarkably, it delivers an energy density of 40.5 Wh kg−1 and a high power density of 3760.7 W kg−1.