A novel polyelectrolyte-functionalized ionic liquid (PFIL)/poly(4-styrene sulfonate sodium) (PSS) modified electrode composed of the coaxial and coplanar working, reference and counter electrodes, was used to electropolymerize the polypyrrole. The PFIL/PSS was modified on the integrated electrode (IE) and connected by the working, reference and counter electrodes, resulting in an available charge transfer and lower Ohmic potential drop between the working and counter electrodes. Then polypyrrole (PPy) film was successfully prepared electrochemically without any participation of supporting electrolytes, only in a pyrrole monomer solution. The resulting PPy film in PFIL/PSS matrix exhibited a preferable electroactivity. Subsequently, influence of the modifications on the formation of PPy was further discussed. The results indicated that the synergetic cooperation of PFIL and PSS components accomplished such a successful electropolymerization of PPy.