In this work, polyacrylonitrile (PAN) and carbon nanofibers with controllable nanoporous structures were successfully prepared via electrospinning technique. For the preparation of porous PAN nanofibers, two kinds of polymers of PAN and polyvinylpyrrolidone (PVP) were used as electrospun precursor materials, and then the bicomponent nanofibers of PAN and PVP were extracted with water to remove the PVP in the composite polymer nanofibers. By altering the ratio of PAN/PVP in the precursor, the pore size and pore distribution of porous PAN nanofibers could be easily controlled. By using the porous PAN nanofibers as structures directing template and through heat treatment, carbon nanofibers with nanoporous structures were obtained. The porous nanofibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), differential thermal analyses (DTA), Brunauer-Emmett-Teller (BET) nitrogen adsorption, X-ray diffraction (XRD), and Raman spectra.