Crosslinked polysulfone/polyhedral oligomeric silsesquioxane (POSS) hybrid networks were synthesized in this work by photoinduced copolymerization of polysulfone dimethacrylate (PSU-DMA) and multifunctional POSS-methacrylamide (POSS-MAAm) with various feed ratios. The morphology of the nanocomposites was investigated by transmission electron microscopy (TEM), which suggests the random dispersion of POSS in the PSU matrix without macroscopic agglomeration. Thermogravimetric analysis results confirmed that the thermal stability and char yield of PSU-DMA/POSS-MAAm nanocomposites increased with the increase of POSS loading. Enhanced glass transition temperatures and storage modulus of the networks were observed to be higher than its precursor polymer. Polysulfone-based hybrid networks containing various POSS loadings are synthesized by photoinduced copolymerization of polysulfone dimethacrylate and multifunctional POSS-methacrylamide. While TEM results suggest the random dispersion of POSS in the polymer matrix, thermal and dynamic mechanical analyses clearly confirm the better thermal and mechanic behavior of hybrid networks. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.