Polyacrylonitrile (PAN)/Co(OAc)(2)/carbon nanotubes (CNTs) composite nanofibers were fabricated via electrospinning with N, N-dimethylformamide (DMF) as solvent, and by carbonization and activation of the above precursor nanofibers, porous carbon composite nanofibers were successfully obtained. Scanning electron microscope, X-ray diffraction, ASAP 2020, and Solartron 1470 were used to characterize the surface morphology, the phase composition, specific surface area, and electrochemical property of the nanofibers, respectively. The result showed that some of the fibers were broken after sintering, and the surface area and pore volume of the porous C/Cu/CNTs were 771 m(2)/g and 0.347 cm(3)/g, respectively. The specific capacitance of the composite nanofibers reached up to 210 F/g at the current density of 1.0 A/g. Its energy density and power density were 3.1 Wh/Kg and 2,337 W/Kg, respectively, at the current of 0.5 and 5 mA.