Tethered layered silicates/polyurethane nanocomposites displaying high tensile strength and high elongation to break were synthesized by using reactive swelling-agent-modified silicates as pseudo chain extenders for a polyurethane prepolymer. The dispersion of layered silicates in polyurethane was found to be transformed from an intercalated to an exfoliated structure when the number of hydroxyl groups of the swelling agent increased as evidenced from the transmission electron microscopy and wide-angle X-ray diffraction analyses. The improved morphology of the nanocomposites resulted in an ultrahigh efficiency in enhancing the mechanical properties of polyurethane, despite variations in the molecular weight and in the extent of hydrogen bonding in the hard segment phase. In particular, a 34% increase in Young's modulus, a 1.7-fold increase in the tensile strength, and a 1.3-fold increase in the elongation to break occurred in the nanocomposite of polyurethane containing only 1 wt % trihydroxyl-group swelling-agent-modified silicates as compared to those of pristine polyurethane.