The multi-walled carbon nanotube (CNT)-embedded activated carbon nanofibers (ACNF/CNT) and activated carbon nanofibers (ACNF) were prepared by stabilizing and activating the non-woven web of polyacrilonitrile (PAN) or PAN/CNT prepared by electrospinning. Both ACNF and ACNF/CNT were partially aligned along the winding direction of the drum winder. The average diameter of ACNF was 330 nm, while that of ACNF/CNT was lowered to 230 nm with rough surface. This was attributed to the CNT-added polymer solution in the electrospinning process providing finer fibers by increasing the electrical conductivity compared with the CNT-free one. The specific surface area and electrical conductivity of ACNF were 984m(2)/g and 0.42S/cm, respectively, while those of ACNF/CNT were 1170m(2)/g and 0.98S/cm, respectively. PPy was coated on the electrospun ACNF/CNT (PPy/ACNF/CNT) by in situ chemical polymerization in order to improve the electrochemical performance. The capacitances of the ACNF and PPy/ACNF electrodes were 141 and 261 F/g at 1mA/cm(2), respectively, whereas that of PPy/ACNF/CNT was 333 F/g. This improvement in capacitance was attributed to the following: (i) the preparation of aligned nano-sized ACNF/CNT by electrospinning and the addition of CNT and (ii) the formation of a good charge-transfer complex by the PPy coating on the surface of the aligned nano-sized ACNF/CNT. The former leads to a good morphology and superior properties, such as a higher surface area, the formation of mesopores and an increase in electrical conductivity. The latter offers a refined three-dimensional network due to the highly porous structure between ACNF/CNT and PPy. (C) 2008 Elsevier Ltd. All rights reserved.