A nanoporous polyhedral oligomeric silisesquioxane (POSS) containing eight epoxy functional groups [octakis(dimethylsiloxypropylglycidyl ether)silsesquioxane, OG] reacts with meta-phenylenediamine (mPDA) to form epoxy resin network with nanostructures. The glass transition temperature (T-g) of the cured OG/mPDA product is significantly higher than that of the diglycidyl ether of bisphenol A (DGEBA) cured with mPDA (DGEBA/mPDA) material due to the presence of the POSS cages that is able to effectively hinder the motion of the network junctions. The cured OG/mPDA product inherently possesses higher thermal stability than the cured DGEBA/mPDA product based on higher maximum decomposition rate temperature, and higher char yield of the former. However, the existence of large fraction of the unreacted amine groups causes lower initial decomposition temperature of the OG/mPDA because it tends to decompose or volatilize on heating at relatively low temperature. The dielectric constant of the OG/mPDA material (2.31) is substantially lower than that of the DGEBA/mPDA (3.51) as a consequence the presence of nanoporous POSS cubes in the epoxy matrix. (C) 2004 Elsevier Ltd. All rights reserved.