A nonaqueous dispersion of poly(3,4-ethylenedioxythiophene) (PEDOT) was prepared with the use of polymeric ionic liquid (PIL) as a polymerization template and phase transfer medium. A detailed investigation was performed to understand the role of PIL in the course of polymerization and phase transfer reaction. On the basis of our findings from X-ray photoelectric spectroscopy (XPS), we propose a mechanism by which the PIL leads to the nanostructured PEDOT colloids in various organic solvents and thus facilitating smoother surface morphologies of the PEDO-PIL PIL films. In addition, the enhancement of charge transport was observed for PEDOT-PIL complex when compared with PEDOT without PIL. Raman spectroscopy indicates that there is a reduced interaction between the charge carriers on the PEDOT and the counter ions bound to PIL, thus promoting charge carrier hopping rates. (c) 2008 Wiley Periodicals, Inc.