In this work, polyaniline (PANI) nanofibrous networks were prepared using ionic liquid (IL), 1-hexadecyl-3-methylimidazolium chloride (C16MIMCl), as a template through oxidative polymerization of aniline with ammonium persulfate. The resulting PANI was characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis, and FTIR. It was indicated that the as-prepared PANI was in the emeraldine form and its morphology strongly depended on the molar ratio of aniline/C16MIMCI. A possible mechanism for the formation of PANI nanofibrous networks was that the ordered micro-domains of the IL acted as template to direct the growth of the nanostructures.