The ionic materials were added to PEDOT/PSS solution as secondary dopants. The conductivity of PEDOT/PSS film improved with adding ionic materials. The film of PEDOT/PSS with 1% pyridinium p-toluene-sulfonate showed the conductivity of 23S/cm, which is increased about three orders than the film of origin PEDOT/PSS with 0.028S/cm. The surface morphology of films of PEDOT/PSS mixture is investigated by atomic force microscope. The AFM showed the increasing of grain size with the addition of pyridinium p-toluene-sulfonate.