Carbon nanofibers have been investigated for the electrode material applications of energy storage devices. In this study, aromatic poly(ether amide) (PEA)-based CNFs were fabricated as the electrode materials via electrospinning and following carbonization. For the purpose, PEA was mixed with poly(vinyl pyrrolidone) for the efficient electrospinning and effective pore-forming, and as-spun PEA/PVP-nanofibers were carbonized at different temperatures. The morphology and microstructural features of PEA-based CNFs fibers were characterized by using electron microscopy, X-ray diffraction, and BET tests. The electrical conductivity and electrochemical properties of the CNFs were investigated with aids of electrical conductivity meter, cycle voltammetry, galvanostatic charge-discharge test. The electrochemical performance such as specific capacitance, energy density and powder density of the CNFs was analyzed by considering the microstructural features including pore size, surface area, etc.