X-ray photoelectron spectroscopy (XPS) was used to analyze the composition of films at different deposition parameters of sputtered Al-Ce coatings on AA6061 aluminum alloys. By means of electrochemical impedance spectroscopy (EIS) measurements, the protective character of these coatings was studied for 21 days of exposure in a 3.5 wt% NaCl solution and an attempt was made to establish the relationship between film thickness and chemical composition (Al/Ce, Ce-3/Ce4+ ratios) of the surface before and after the electrochemical characterization. XPS studies revealed the presence of the Al-o, Al2O3, CeO2 and Ce2O3 compounds, confirming that the sputtered Al-Ce films were deposited in the metallic form and thereafter were superficially oxidized under ambient conditions. The Al-Ce bonds were overlapped with the signal of cerium oxides. The transport phenomena in the oxide film or controlled diffusion process are strongly dependent on the deposition parameters and exposure time in the aggressive medium. It was also found that in the deposited samples at p(4)P(200)t(300), the film was still present after 21 days of exposure, although with visible cracks and erosion areas; however, the Ce-3/Ce4+ ratio almost remained constant before and after the electrochemical characterization, which explained the barrier properties of these samples as compared with others at different deposition parameters.