Core level and valence band x-ray photoelectron spectroscopy are used to study the chemical composition of the surface films on aluminum alloys. Certain alloying elements may preferentially migrate to the surface of an alloy, thereby altering the composition and consequently the chemistry of the surface. The behavior of a 6061 aluminum alloy is compared with that of pure aluminum. It is shown that the type of magnesium film formed at the alloy surface can be determined by comparing the valence band spectra of the aluminum alloy surface with that of known magnesium and aluminum compounds. The experimental valence band spectra of these compounds are supported by spectra generated from band structure calculations. The effect of boiling water on the surface film is discussed, with significant differences in surface chemistry being seen for the metal and the alloy.