Frontal polymerization (FP) has been successfully applied, for the first time, to obtain polymeric nanocomposites containing polyhedral oligomeric silses-quioxanes (POSS) in an amine-cured epoxy matrix. Variations of maximum temperature (T-max) and front velocity (V-f) have been studied. A comparison of these products with the corresponding materials, obtained by the classical batch polymerization technique, demonstrated that FP allows a higher degree of conversion than batch polymerization. The products have been characterized in terms of their thermal behavior with DSC analysis. SEM and X-ray analyses revealed the morphology and the structures of the nanocomposites. The nanocomposites obtained by FP have the same characteristics of those synthesized, in much longer times, by batch polymerization. (c) 2007 Wiley Periodicals, Inc.