The oxidation of an amorphous TiAlN coating has been studied by in situ direct recoil spectroscopy (DRS) and mass spectroscopy of recoiled ions (MSRI) and ex situ x-ray photoelectron spectroscopy (XPS). DRS and MSRI monitored the changes in surface composition as the sample was heated to 460 °C under an 18O2 pressure of 10-6 Torr. Angular resolved XPS data were acquired for thickness-dependence information. The initial surface was partially oxidized from air exposure. Both DRS and XPS showed the Al-rich near surface and the presence of N in the subsurface. As shown by DRS and MSRI, oxidation at elevated temperatures yielded surface nitrogen loss and Ti enrichment. XPS confirmed the preferential formation of TiO2 on the surface. This study also provides a comparison between the direct recoil (neutrals and ions) and the ionic recoil signals. In our conditions, the negative ionic fraction of all elements except H tracks their true surface content variations given by DRS. The results were compared with early work performed on identical samples. In this case the TiAlN film was oxidized with an O2 pressure in the mTorr range and the surface changes are followed in situ by positive MSRI and XPS. This experiment also indicates that Al and N are buried under TiO2 but from 600 °C. © 2002 American Vacuum Society.