Li–Al–O materials are interesting for several applications. Herein, a Li–Al–O thin‐film materials library, deposited by inert magnetron sputtering and postdeposition annealing in O2 atmosphere, is used to study the effects of different annealing temperatures (300–850 °C) and durations (1 min to 7 h) on crystallinity and composition of the films. X‐ray photoelectron spectroscopy depth profiling reveals inhomogeneous compositional depth profiles of conventionally annealed films (300–650 °C, 3–7 h) with increased Li contents toward the film surface and increased Al contents toward the film–substrate interface, as confirmed by a combination of Rutherford backscattering spectrometry and deuteron‐induced nuclear reaction analysis. The minimum temperature for the formation of crystalline LiAlO2 in the otherwise amorphous films is 550 °C. The undesired inhomogeneous depth profiles are transformed into homogeneous ones by rapid thermal annealing (750–850 °C, 1–10 min), while simultaneously causing the formation of crystalline LiAlO2. Therefore, rapid thermal annealing is shown to be more suitable than conventional annealing for the thermal processing of Li–Al–O thin films. Moreover, this conclusion is expected to have broader relevance beyond Li–Al–O materials, as it is likely to apply to other Li metal oxides, of which there are many technologically relevant ones.