We address herein the question of the termination of the Al-terminated α-Al 2 O 3 (0001) surface. Over decades, various analyses made by different groups repeatedly suggested the presence of a residual coverage of surface OH groups on Al 2 O 3 crystals and powders after annealing in vacuum. However, other authors came to contrary conclusions, thus maintaining a persistent blur on the issue. The present work examines the Cr/alumina interface via Cr K absorption edge analysis (Extended X-Ray Absorption Fine Structure and X-ray Absorption Near Edge Structure) and photoemission with the support of density functional (DFT) calculations. Experiments support the presence of surface OH groups to account for the observed environment as well as the oxidation state of Cr adatoms (Cr 3+). Following a comprehensive DFT-based analysis of Cr z+-O n H m configurations (z=0 to 6, n and m=0 to 3), the Cr 3+-O 2 H alumina-supported surface moieties are found to successfully fit the XAS edge calculations. Most importantly, the combination of experiment and theory that is developed unambiguously demonstrates the presence of surface OH groups on α-Al 2 O 3 (0001) after annealing in vacuum.