X-ray Photoelectron Spectroscopy (XPS), X-ray Absorption Fine Structure spectroscopy (XAFS), X-ray Diffraction (XRD) and Pyridine Adsorption Spectroscopy (PAS-S) were used to investigate the solid superacid high surface area AIF3 (HS AIF3). The aim of this work was to establish correlations between Lewis acidity, surface area, geometric and electronic structure of the materials. The aim of this study was to obtain structure/activity relationships for AIF3 materials synthesised by different routes, with a view to future tailoring of the properties of these materials to potential industrial applications.