AbstractNanocomposites of waterborne polyurethane (WPU) containing graphene oxide sheets (GO) were prepared by an in-situ polymerization method at low temperature. The morphology and interface structure were characterized by atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Without undergoing complicated functionalization processes, GO can be finely embed into a WPU matrix and present high degree of orientation at high GO contents, due to the formation of chemical bonds and hydrogen bonding. From the Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and dynamic mechanical analysis (DMA) results, incorporation of GO exists in two ways and shows inverse effects. At a content of 2.0 wt.% GO loading, the tensile elastic modulus of the GO-WPU film increased by 193% to neat WPU. The nanocomposites also displayed 30°C higher thermal stability than WPU in thermogravimetric (TG) curves. This environment-friendly method may pave the way to design graphene-based polymer composites.