Polyurethane (PU)/Dodecyl sulphate intercalated layered double hydroxide (DS-LDH) nanocomposites were successfully synthesized from PU prepolymer and polyol TG (mixtures of glycerol and trimethylolpropane) for the first time. Formation of partially exfoliated structures of PU/DS-LDH nanocomposites was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Analysis of tensile properties showed significant improvements in tensile strength (TS) and elongation at break (EB) of about 407% and 83% for PU/DS-LDH (3 wt%) nanocomposite. The observed excellent concurrent improvement in TS and EB is attributed to the relatively better reinforcing effect of partially exfoliated DS-LDH layers in PU making the present investigation most noteworthy. In addition, gradual improvement in thermal stability and limiting oxygen index (LOI) with increasing DS-LDH loading makes these nanocomposites versatile and hence suitable for many critical applications.