In the present study, electrically conducting carbon nanofiber (CNF) mats were produced by incorporating tetraethoxy orthosilicate (TEOS) into polyacrylonitrile (PAN) via electrospinning. A simple thermal treatment was applied to the electrospun nanofibers to create ultramicropores that could accommodate a large number of ions were formed on the surface of the CNFs, removing the need for a time-consuming activation step. The Si/CNF composites showed high capacitance and energy/power density values due to the formation of ultramicropores and the introduction of heteroatoms. (C) 2011 Elsevier B.V. All rights reserved.