Organic-inorganic nanocomposites were designed by combining a commercial epoxy resin (diglycidyl ether of bisphenol A - DER) and a multi-thiol crosslinking agent with a "clickable" polyhedral oligomeric silsesquioxane (POSS) compound. 1-methylimidazole was employed as a catalyst to yield highly efficient thiol-Michael addition reaction materials. The equivalent ratio between epoxy: thiol was maintained 1:1 in all the formulations and therefore the homopolymerization reaction of epoxy resin is unlikely to occur. The synergistic effect of the thiol compound and mono-functionalized POSS bearing one epoxy/thiol reactive group on the curing process was investigated in detail. We assume that the mechanistic pathway of the thiol-epoxy click-reaction increases in complexity due to the introduction of reactive POSS in the system. The incorporation of mono-epoxy or mono-thiol POSS in the thiolepoxy organic host leads to distinct thermo-mechanical behavior of the crosslinked networks due to the fact that the POSS compound will chemically interact in the click reaction. (C) 2018 Elsevier Ltd. All rights reserved.