In situ infrared ͑IR͒ spectroscopy and visible-light ͑VIS͒ spectroscopic ellipsometry over the spectral range from 700 to 2000 cm Ϫ1 and 1.5-3.5 eV, respectively, were used to investigate the optical behavior of boron nitride ͑BN͒ thin films at temperatures from room temperature ͑RT͒ to 600°C. The polycrystalline hexagonal ͑h͒ and mixed-phase h-and cubic (c)-BN thin films were deposited by magnetron sputtering on ͓001͔ silicon. We observe a reversible moisture incorporation process in as-grown h-BN samples. When stored in normal ambient, the h-BN thin films absorb water into thin-film micropores. When annealed in ultrahigh vacuum or a dry nitrogen atmosphere, the samples expel moisture but retain their microstructure. This is observable by reduction of the thin-film refractive indices in accordance with changes in the IR lattice resonance behavior. The optical properties of high c-BN content thin films remain unchanged during annealing. And both intrinsic h-and c-BN thin-film VIS refractive indices are nearly temperature independent, at least up to 600°C. Therefore, RT BN optical constants can be used for feedback loop control in in situ thin-film growth at temperatures up to 600°C. ͓S0021-8979͑98͒07613-0͔