Chronoamperometry technique was used to prepare polypyrrole onto low alloy steel surface from aqueous solutions. The morphology and composition of the as-obtained deposit was characterized by scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared techniques. The dendritic polymer could be realized at the high potential and favorable mass transfer conditions. Contact angle tests proved that the polypyrrole with rough surfaces had small contact angles. After the modification with the 1H, 1H, 2H, 2H-perfluorooctyl trichlorosilane, the values of contact angles of polypyrrole reached up to ca. 130°. The consequent infusion of perfluorinated lubricant into the hydrophobic matrix led to a composite material. Potentiodynamic polarization tests in 3.5 wt % NaCl solution revealed that low alloy steel covered with this composite material raised the corrosion potential more than 1000 mV and decreased the corrosion current density ca. 3 orders, suggesting that the perfluorinated lubricant/ polypyrrole composite material behaved as a good candidate for corrosion inhibition. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40184.