Heterogeneous catalysts, investigated by several techniques, such as XRD, XPS, TEM, TPR/TPO, able to ascertain their structural, chemical, electronic and morphology properties are reviewed with respect to selected results obtained by the group during approximately the last twenty five years. The field of application covers different catalytic processes such as alkene hydrogenation over noble metal catalysts, hydrodesulfurization (HDS) and environmental catalysis. In particular the following subjects are described: the peculiarity of a support like pumice, in relation to the hydrogenation activity of the supported noble metals; supported gold and supported gold containing alloy catalysts for different types of reactions; the importance of the CoMoS precursors and the structure of bimetallic PdAu and PtAu for hydrotreating processes; the effect of a sulfatable oxide, such as TiO2, on the CH4 oxidation activity of supported Pd catalysts; different preparation methods influencing significantly the catalytic behavior of supported nickel catalysts for methane conversion processes. The reviewing of the different case studies illustrates the importance of the interaction between support and active metals ultimately determining the surface distribution of the active sites and their final catalytic activity. (C) 2016 Elsevier B.V. All rights reserved.