A non-aqueous sol-gel Al-based fluoride has been subjected to the microwave solvothermal process. The final material depends on the temperature heat treatment used. Three types of material have been prepared: 1) for low temperature heat treatment (90 °C) X-ray amorphous alkoxy fluoride was obtained; 2) for the highest temperature used (200 °C) the metastable form -AlF3 was obtained with a very large surface area of 125 m2 g-1. The mechanism of the amorphouscrystalline transformation has been rationalised by the occurrence of a decomposition reaction of the gel fluoride induced by the microwave irradiation. 3) Finally, at intermediate temperature (180 °C) a multi-component material mixture exhibiting a huge surface area of 525 m2 g-1 has been obtained and further investigated after mild post-treatment fluorination using F2 gas. The resulting aluminium-based fluoride still possesses a high-surface-area of 330 m2 g-1. HRTEM revealed that the solid is built from large particles (50 nm) identified as -AlF3, and small ones (10 nm), relative to an unidentified phase. This new high-surface-area material exhibits strong Lewis acidity as revealed by pyridine adsorption and catalytic tests. By comparison with other materials, it has been shown that whatever the composition/structure of the Al-based fluoride materials, the number of strong Lewis acid sites is related to the surface area, highlighting the role of surface reconstruction occurring on a nanoscopic scale on the formation of the strongest Lewis acid sites.< Réduire