In this study, a hybrid electrode material for supercapacitors based on hierarchical porous carbon fiber@vanadium nitride nanoparticles is fabricated using the method of phase-separation mediated by the PAA-b-PAN-b-PAA tri-block copolymer. In the phase-separation procedure, the ionic block copolymer self-assembled on the surface of carbon nanofibers, and is used to adsorb NH4VO3. Thermal treatment at controlled temperatures under an NH3 : N2 atmosphere led to the formation of vanadium nitride nanoparticles that are distributed uniformly on the nanofiber surface. By changing the PAN to PAA-b-PAN-b-PAA ratio in the casting solution, a maximum specific capacitance of 240.5 F g-1 is achieved at the current density of 0.5 A g-1 with good rate capability at a capacitance retention of 72.1% at 5.0 A g-1 in an aqueous electrolyte of 6 mol L-1 KOH within the potential range of -1.10 to 0 V (rN/A = 1.5/1.0). Moreover, an asymmetric supercapacitor is assembled by using the hierarchical porous carbon fiber@vanadium nitride as the negative electrode and Ni(OH)2 as the positive electrode. Remarkably, at the power density of 400 W kg-1, the supercapacitor device delivers a better energy density of 39.3 W h kg-1. It also shows excellent electrochemical stability, and thus might be used as a promising energy-storage device.