Electrically conducting nanofiber mats of polyaniline/copolyacrylonitrile (PANI/ PAN) blend in NMP were successfully fabricated using electrospinning technique. Morphology and diameter of the nanofibers were studied by scanning electron microscope. Structural characteristics of the electrospun nanofibers were examined using differential scanning calorimetry, Fourier transform infrared spectroscopy and X-ray diffraction. Electrical of the electrospun mats was examined. The PANI/PAN blends containing up to the 30% PANI could be electrospun into the continuous fibrous structure, although pure PANI solution was not able to be electrospun into the fibrous structure. The formation of the hydrogen bonding between PAN copolymer and the PANI was predicted by the FT-IR spectra. DSC analysis showed only one Tg for the blend nanofibers, implying compatibility of the two components in the blend. X-ray diffraction showed that the crystalline peaks of PANI almost were disappeared in the PANI/PAN blends. The results of electrical conductivity measurements showed that the electrical conductivity of the blend increased with the increase in PANI content with percolation threshold of around 0.5 wt%.