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Two fluorinated γ-Al 2 O 3 series were synthesized by a sol-gel method with two solvents (2-propanol and 2-butanol), two aluminium sources (ATB and ATP) and one fluorine source (Na 3 AlF 6 ). The resulting inorganic matrixes were evaluated to characterize aluminium and fluorine species ([AlO 4 5- ], [AlO 5 7- ], [AlO 6 9- ], [AlF 4 - Al MAS-NMR) and infrared spectroscopy (IR-ATR). BET and BJH analyses using the nitrogen isotherms of these materials allowed identifying a clear trend in some textural parameters such as specific surface area and fluorine content. These results were confirmed by scanning electron microscopy (SEM). Chemical affinity and acid surface properties were evidenced with colour shifts in two groups of hybrid pigments, prepared with natural anthocyanins ( 5 2- ] and [AlF 6 3- ]) by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), 27 Al magic angle spinning nuclear magnetic resonance ( 27 Al MAS-NMR) and infrared spectroscopy (IR-ATR). BET and BJH analyses using the nitrogen isotherms of these materials allowed identifying a clear trend in some textural parameters such as specific surface area and fluorine content. These results were confirmed by scanning electron microscopy (SEM). Chemical affinity and acid surface properties were evidenced with colour shifts in two groups of hybrid pigments, prepared with natural anthocyanins ( Brassica oleracea ) and betacyanins ( Bougainvillea glabra ).