Heteroatom-doped mesoporous carbon nanofibers (HMCNFs) were prepared by direct carbonization of highly cross-linked organic inorganic hybrid polymeric nanofibers (PNFs) under an inert atmosphere. The HMCNFs were of large Brunauer-Emmett-Teller (BET) surface area, uniform mesopore (with diameter 4 nm), and high content of heteroatoms. Electrodes prepared by using HMCNFs showed a high specific capacitance of 214.9 F/g in 6 M KOH electrolyte, because of the large BET surface area and high content of heteroatoms. This work involved preparation of carbon nanofibers from a novel precursor and used the nanofibers in the fabrication of high-performance supercapacitor electrodes. (C) 2015 Elsevier B.V. All rights reserved.