Conductive microfibers with an average diameter of ca. 1.0 mu m were prepared by in situ polymerization of aniline, in which poly(vinylchloride-acrylonitrile) (PVC-AN) was used as the filament-material in electrospinning to form precursor microfibers and carry the aniline monomers. Fourier-transform infrared (FTIR) results demonstrated that PANi was successfully polymerized in the microfibers. The morphology of the PVC-AN-PANi microfibers was observed by scanning electron microscopy (SEM). Results of differential scanning calorimetry indicated that the polymer composite of PVC-AN-PANi formed via molecular interactions. Although the conductivity of PVC-AN-PANi microfibers was still limited (2.2 x 10(-8) S/cm), this method provided an effective and convenient approach for preparing highly uniform and soft microfibrous electrodes. (C) 2013 Xiao-Qiang Li and Ming-Qiao Ge. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.