In order to synthesize chemical filters for the selective removal of volatile fluorides, commercial magnesium fluoride MgF2 with high specific surface area (HSA) was investigated. The amount of -OH groups substituting fluorine is not negligible, partly due to the high surface area, but also due to the synthesis route. These hydroxyl groups induce a Lewis basicity on the surface of metal fluorides. The amount of these Lewis basic sites has been tailored using fluorination with F2 gas. The sorption of VOF3, used as model gas, onto these fluorides was investigated. The versatility of surface chemistry as a function of a number of Lewis basic sites opens the way to filter selectivity mixture of volatile fluorides depending on their Lewis acidity. HSA MgF2 acts as a stable matrix towards the gas to be purified, and the selectivity may be achieved by a higher Lewis acidity of the gaseous impurity.