Summary Cubic silsesquioxanes offer access to organic/inorganic hybrids. A system formed by a polyhedral oligomeric silsesquioxane (POSS) with eight epoxy reactive groups per molecule, octaepoxycyclohexyldimethylsilyl-POSS, cured with an aliphatic diamine (bisaniline) was studied in different ratios. The characterization of the POSS was carried out by differential scanning calorimetry (DSC) and thermogravimetry (TG). The distribution of species in the reaction of the mixtures POSS/diamine was followed by gel permeation chromatography (GPC). The degradation was studied by thermogravimetric analysis.