The deposition of cerium-rich films on copper under cathodic polarization was studied as a model system for understanding the mechanism of corrosion inhibition of copper-containing aluminum alloys. Deposition was also studied on gold and. iron for comparison with copper. Inhibition of corrosion of the aluminum alloys is achieved by deposition of a cerium-rich film on the copper-containing intermetallics that blocks the cathodic reduction of oxygen at these sites. X-ray absorption near-edge structure measurements show that cerium-rich films precipitated from aerated solutions are in the tetravalent state. Thermodynamically, the Pourbaix diagram predicts that under these conditions cerium should be in the trivalent state. This indicates that cerium chemistry is determined by processes in the solution rather than the potential of the electrode. Cerium-rich film formation is dependent on reduction of oxygen which influences the oxidation of Ce(III) to Ce(IV) in solution and precipitation of the film by changing the local pH at the electrode. The generation of hydrogen peroxide by oxygen reduction is considered to enhance cerium-rich film formation by oxidizing Ce(III) to Ce(IV) in solution. This was confirmed by addition of hydrogen peroxide to the solution.