The hybrid electrode material of carbon fiber and vanadium nitride (CF@VN) is fabricated from waste metal ions absorbed on the recycled cigarette butts under the mixed atmosphere of NH3 and N2 at 800°C for supercapacitors. The microstructures and morphologies of CF@VN are characterized by X-ray diffraction, scanning electron microscopy, and BET methods; and the electrochemical properties are investigated by cyclic voltammetry, galvanostatic charge/discharge, and impedance spectroscopy, respectively. The results demonstrate that the CF@VN material is in nanoscale with hierarchical porous structure, and the high specific capacitance of 104.05Fg−1 is obtained at the current density of 0.5Ag−1 in 2M KOH aqueous electrolyte. The asymmetric supercapacitor is assembled by using CF@VN as negative electrode and activated carbon as positive electrode, which exhibits the maximum specific capacitance of 23.28Fg−1 at current density of 0.5Ag−1 with the potential range of 0 to 1.6V with about 82% of capacitance retention rate after 1000 cycles at a current density of 1Ag−1. In addition, there is a wide utilization of the recycled cigarette butts in absorbing the other metal nitrides, such as Fe3+, Co2+, and Ni2+ ions, for application in supercapacitors.