In this article, the high potential of the fluorolytic sol-gel process to synthesise nanoscopic metal fluorides with different acid-base properties is shown. These nanoscopic materials exhibit high potential to be used as heterogeneous catalysts due to their high surface areas and their tunable surface properties. Thus, for each specific reaction the required surface properties of the catalysts can be "adjusted" to achieve a high yield and selectivity of the desired product. As a consequence, a greener method of chemical production can be accomplished. Moreover the cheap and easy synthesis of the catalysts using basic chemicals not only makes them interesting for fundamental research but also provides an easy transformation to industrial applications. (C) 2009 Elsevier B.V. All rights reserved.