The adsorption behavior of gamma-GPS on low carbon steel surfaces was systematically investigated by reflection absorption infrared spectroscopy (RA-IR), electrochemical impedance spectroscopy (EIS) and atomic force microscopic (AFM), focusing on the changes in gamma-GPS chains alignment during the adsorption process and the influence of assembly time on the chemical structures, three-dimension morphology and corrosion resisting property of gamma-GPS films. The results indicated that the adsorption of gamma-GPS exhibited an oscillatory phenomenon, which experienced rapid adsorption firstly, then reached maximum adsorption capacity, subsequently suffered extensive desorption, finally went through irreversible slow adsorption. The growth behavior and protective performance of gamma-GPS films was closely related to the adsorption capacity and the alignment of silanol monomers. As more silanol monomers were adsorbed, the stronger the intermolecular van der Waals interactions between the gamma-GPS chains would be, resulting in highly ordered gamma-GPS films with excellent performance. The proposed adsorption models were used to simulate the experimental phenomena and determine the adsorption mechanisms taking place on the low carbon steel surfaces. (C) 2011 Elsevier B.V. All rights reserved.