Aluminas are strategic materials used in many major industrial processes, either as catalyst supports or as catalysts in their own right. The transition alumina γ‐Al₂O₃is a privileged support, whose reactivity can be tuned by thermal activation. This study provides a qualitative and quantitative assessment of the hydroxyl groups present on the surface of γ‐Al₂O₃at three different dehydroxylation temperatures. The principal [AlOH] configurations are identified and described in unprecedented detail at the molecular level. The structures were established by combining information from high‐field¹H and²⁷Al solid‐state NMR, IR spectroscopy and DFT calculations, as well as selective reactivity studies. Finally, the relationship between the hydroxyl structures and the molecular‐level structures of the active sites in catalytic alkane metathesis is discussed.

Aluminas are strategic materials used in many major industrial processes, either as catalyst supports or as catalysts in their own right. The transition alumina γ‐Al₂O₃is a privileged support, whose reactivity can be tuned by thermal activation. This study provides a qualitative and quantitative assessment of the hydroxyl groups present on the surface of γ‐Al₂O₃at three different dehydroxylation temperatures. The principal [AlOH] configurations are identified and described in unprecedented detail at the molecular level. The structures were established by combining information from high‐field¹H and²⁷Al solid‐state NMR, IR spectroscopy and DFT calculations, as well as selective reactivity studies. Finally, the relationship between the hydroxyl structures and the molecular‐level structures of the active sites in catalytic alkane metathesis is discussed.