Porous poly(vinylidene fluoride) fibers were prepared by electrospinning from solutions in dimethylformamide, poly(ethylene oxide) (PEO) and water. The PVDF fiber mats were then converted into electrospun carbon fiber paper using a low temperature chemical stabilization treatment ("dehydrofluorination") followed by carbonization at 1000 degrees C. The resulting self-supporting carbon fiber paper exhibits unusually high surface area, in excess of 380 m(2)/g as measured by the nitrogen adsorption method, and a hierarchical pore structure. The largest pores are formed by the interstices between fibers; intermediate-sized pores arise from liquid-liquid phase separation during electrospinning to form polymer-rich and solvent-rich domains within the fibers; the smallest pores form upon decomposition of the PEO during carbonization. The electrospun carbon paper performs well as an electrode for driving the redox chemistry of ferrocene/ferrocenium. This is attributed to the high surface area of the electrode and the ease of diffusion of the redox-active species within the porous structure. The ratio of the dehydrofluorination agent (1,8-diazabicyclo[5.4.0]undec-7-ene) to vinylidene fluoride during dehydrofluorination was found to be the key to retaining the as-spun pore morphology during carbonization. The structure and morphology were further characterized by Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, X-ray diffraction, and Raman spectroscopy. (C) 2011 Elsevier Ltd. All rights reserved.