In this study, waterborne graphene oxide/poly(siloxane-urethane)s (GO/SWPUs) nanocomposites were in situ synthesised. Therein, siloxane units facilitated the crosslinking of polyurethanes, and GO imparted the nanocomposites with special functions. With increasing GO content, the average particle size, viscosity, and ionic conductivity of the GO/SWPU dispersion increased, but the absolute value of the zeta potential decreased; this was due to ionic interactions between the COO-NH+(C2H5)(3) ions of the SWPU and COO-H+ ions of the GO. The surface roughness of the GO/SWPU film was larger as GO content was higher, which was due to a strong interaction between the GO and SWPU phases. Increasing the GO content improved the thermal resistance, dynamic glass transition temperature, and tensile strength of the GO/SWPU film, but adding more than 0.1 wt% GO yielded unfavourable results. Thus, adding GO improved the thermal and mechanical properties of the GO/SWPU nanocomposites, but this improvement was observed only up to a certain GO concentration, possibly because of the agglutination of GO in SWPU. In addition, the surface and volumetric electrical resistivities of the GO/SWPU nanocomposites decreased when the GO content were increased.