For free-standing and self-doped electrode materials of energy storage devices, in this study, we investigate the microstructures and electrochemical properties of aromatic poly(ether amide) (PEA)-derived carbon nanofibers (CNFs), which are manufactured by electrospinning mixed solutions of PEA and poly(vinyl pyrrolidone) (PVP) at three different compositions and carbonization of the as-spun nanofibers at 1000 °C. The scanning electron microscopy, energy dispersive spectroscopy, Raman spectroscopy, and elemental analyses reveal that PEA-derived CNFs have a unique interfused network structure with nitrogen self-doped and quasi-ordered graphitic features. Accordingly, a high apparent electrical conductivity of 3.72−7.79 S/cm is attained for the CNFs. The cyclic voltammetry and galvanostatic charge−discharge measurements confirm that PEA-derived CNFs have excellent electrochemical properties in terms of a specific capacitance of ∼249.0 F/g at 1.0 A/g, power density of 10,000−1,000 W/kg, energy density of 30.1−69.1 Wh/kg, capacitance retention of ∼79%, and Coulombic efficiency of ∼92% after 3000 cycle tests. These results indicate that PEA-derived CNFs can be used as highly stable, self-supporting, and doping-free electrode materials for high-performance energy storage devices.