To develop economical and high-performance supercapacitor electrodes in an aqueous electrolyte, polyacrylonitrile (PAN)/pitch/lignin-based carbon nanofibers (CNFs) with ZnO (PPL-Zn) are successfully fabricated by one-step electrospinning of PAN, pitch, lignin, and zinc acetate. The oxygen-rich lignin in the PPL-Zn electrodes induces porosity on the fiber surface by eliminating many functional groups such carboxylic, carbonyl, hydroxyl and ketone and organic moieties in the simple heat treatment without any activation agent/activation process. Moreover, the many aromatic components, high carbon content, and low glass transition temperature of lignin are excellent precursors to CNF composites. In addition to lignin, pitch is used as a precursor to CNF to reduce the cost and increase the carbon yield and electrical conductivity of the CNFs. These characteristics afford PPL-Zn(5) (5 wt% of zinc acetate relative to PAN and lignin) with good capacitive behavior for application as supercapacitor electrodes with a maximum specific capacitance of 165 Fg-1 at 1 mAcm−2 with a capacitance retention of 88%, high energy densities of 22–18 Whkg−1 in the power density range of 400 to 10,000 Wkg-1, and excellent cycling performance reduced by only ∼6% after 3000 cycles of charge/discharge due to the synergistic effect of the electrical double layer and the pseudocapacitive effect.