Polyhedral oligomeric octa(propargylaminophenyl)silsesquioxane (OPAPS) was used to prepare composite resins with prepolyarylacetylene (prePAA). The curing and thermal behaviors of the PAA/OPAPS composites were studied through Fourier-transform infrared (FTIR), X-ray diffraction (XRD), differential scanning calorimetric (DSC), thermogravimetric (TGA), and scanning electron microscopic (SEM) analysis and by direct observation. The morphologies of the PAA/OPAPS resins proved that there was good compatibility between PAA and OPAPS. FTIR analysis indicated formation of a conjugated diene and aromatic ring groups in the thermal curing process of the resins. DSC analysis implied that the addition of OPAPS to prePAA could decrease the exothermic heat and widen the temperature range in the curing process of prePAA. According to TGA analysis, a 10 wt % addition of OPAPS to PAA can maintain the thermal stability of PAA in N2 atmosphere and somewhat enhance the thermal-oxidative stability. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013