Abstract The influence of fluorination of microcrystalline γ-alumina on the acidity of Lewis sites was studied by quantum chemical cluster model approach. B3LYP and HF/6-31++G( d, p) levels of theory were employed, considering the standard and counterpoise-corrected potential energy surfaces (PESs). Explicit inclusion of dynamical electron correlation effects along with the elimination of the basis set superposition effects in geometry optimization and harmonic vibrational analysis were found to be crucial to reproduce the experimental trends in the shifts of the pyridine ν 19b and ν 8a modes upon fluorination. The acidity of surface-exposed Al-sites was found to increase upon fluorination, which is manifested as a ~ 10% increase of the interaction energies, and also in the characteristics of the electronic density and density Laplacian at the intermolecular bond critical point. Bader analysis of the electronic density has shown that pyridine adsorption on pure and fluorinated γ-alumina can be classified as non-covalent interaction.