We report the effect of adding nonaphenol polyethyleneoxy (10) ether (OP10) into the electropolymerization solution of pyrrole on the tensile strength and structure of the as-prepared polypyrrole (PPy) films. The tensile strength of the PPy film prepared from TsONa aqueous solution with OP10 [PPy(TsO-, OP10)] reaches 127 MPa, which is much stronger than that of the film from usual aqueous solution without OP10 [PPy(TsO-), 27.8 MPa]. The results of elemental analysis indicate that the amount of excess oxygen in PPy(TsO-, OP10) decreased obviously, compared with that in PPy(TsO-). The morphology and structure of PPy(TsO-, OP10) and PPy(TsO-) were also compared by SEM and X-ray diffraction spectroscopy.