Ti/Al2O3 bilayer stacks are used as model systems to investigate the role of atomic layer deposition (ALD) and chemical vapor deposition (CVD) to prepare 30–180 nm thick amorphous alumina films as protective barriers for the medium temperature oxidation (500–600 °C) of titanium, which is employed in aeronautic applications. X‐ray diffraction (XRD), transmission electron microscopy (TEM) with selected area electron diffraction (SAED), and X‐ray photoelectron spectroscopy (XPS) results show that the films produced from the direct liquid injection (DLI) CVD of aluminum tri‐isopropoxide (ATI) are poor oxygen barriers. The films processed using the ALD of trimethylaluminum (TMA) show good barrier properties but an extensive intermixing with Ti which subsequently oxidizes. In contrast, the films prepared from dimethyl aluminum isopropoxide (DMAI) by CVD are excellent oxygen barriers and show little intermixing with Ti. Overall, these measurements correlate the effect of the alumina coating thickness, morphology, and stoichiometry resulting from the preparation method to the oxidation barrier properties, and show that compact and stoichiometric amorphous alumina films offer superior barrier properties.