MF3-doped/MgF2 systems with enhanced Lewis acidity are reported, which are obtained either by the conventional aqueous route of co-precipitation or, by a novel non-aqueous soft chemistry route. The latter gives outstanding high surface areas and exhibits potent Lewis acid catalyst behaviour. The doped solid metal fluorides with dopant metals such as Ga, In, Fe, V are discussed in terms of the modified Tanabe model, which is adopted for metal fluoride systems. The two doped but differently prepared systems are analysed according to their surface characteristics by BET surface area, pore-size distribution and XPS/XAES as well as for the solid state structure by scanning electron microscopy (SEM), XRD and F-19-MAS-NMR. The surface properties were evaluated by photoacoustic IR-spectroscopy of pyridine adsorbates and selected catalytic reactions. The exemplarily investigated GaF3-doped/MgF2 system reveals modified intrinsic properties of the solid mixture culminating in very high surface areas of a structurally distorted mesoporous solid and electrostatic charge rearrangements causing increased Lewis acid sites. (C) 2004 Elsevier B.V. All rights reserved.