In this study, the dielectric and thermal properties of nanostructured epoxy/POSS (Polyhedral Oligomeric Silsesquioxanes) composites were investigated, using a reactive Triglycidylisobutyl-POSS (TGIB-POSS) additive from 1 up to 10 wt%. POSS has been successfully dispersed at a molecular level for low content composites, which show a remarkably improved resistance to corona discharges, with up to 60% less eroded sample volume, along with significantly increased dielectric breakdown strengths and thermal conductivities. Epoxy/POSS composites containing 5 wt% and more of the POSS additive exhibit agglomerations, which have been observed by SEM. Furthermore, dielectric spectroscopy revealed additional interfacial loss peaks for such composites containing 5 wt% POSS and more, in addition to the α-and β-peaks known for epoxy.