Tailoring the chemical structures of a precursor polymer for carbon nanofibers (CNFs) produced by thermal treatment of electrospun nanofibers was studied to prepare the electrodes for electrochemical double layer capacitors (EDLCs). To improve energy storage performance of CNF electrodes, 6FDA-durene nanofibers were crosslinked by a vapor crosslinking method, and subsequently carbonized. Chemical modification via crosslinking was confirmed by FTIR spectra while the conversion of crosslinked 6FDA-durene into carbon was done by Raman spectroscopy. Electrochemical performance of these CNF electrodes was evaluated by assembling coin cells, and the CNFs derived from crosslinked 6FDA-durene nanofibers showed higher specific capacitances, energy densities and cycling stability than those from non-crosslinked ones. It was also shown that CNFs prepared using 1 min crosslinking exhibit the highest energy storage performances, a specific capacitance of 301 F g-1 (at 10 mV s-1), and the maximum energy density of 11.1 Wh kg-1 (at 0.5 A g-1) and power density of 1.8 kW kg-1 (at 6 A g-1). Surface area and porosity of CNFs, which is critical for the performance of EDLC electrodes, were studied by nitrogen adsorption/desorption measurements, and it was clearly seen that surface crosslinking of precursor polymers improved surface properties of the resultant CNFs.