Summary: Octaaminophenyl polyhedral oligomeric silsesquioxane (OapPOSS) was used as a crosslinking agent together with 4,4′‐methylenebis‐(2‐chloroaniline) to prepare polyurethane networks containing POSS. Fourier transform infrared spectroscopy (FT‐IR), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were employed to characterize the POSS‐reinforced polyurethane. The POSS‐containing PU networks displayed enhanced glass transition temperatures (Tgs) and the storage moduli of the networks of the glassy state and rubber plateaus were also observed to be significantly higher than that of the control polyurethane although only a small amount of POSS was incorporated into the systems. The results can be ascribed to the significant nanoscale reinforcement effect of POSS cages on the polyurethane matrix. TGA results showed the thermal stability was also improved with incorporation of POSS into the system.Dynamic mechanical spectra of PU and PU nanocomposites containing POSS.imageDynamic mechanical spectra of PU and PU nanocomposites containing POSS.