AbstractThis investigation reports the synthesis of a new class of polyurethane (PU) based on bis(hydroxyalkyl) polydimethylsiloxane (PDMS) as diol and isophorone diisocyanate as diisocyanate followed by the preparation of PU/layered double hydroxide (PU/LDH) nanocomposite via ex‐situ technique. Nuclear magnetic resonance and Fourier‐transform infrared spectroscopy studies confirm the formation of PU and incorporation of PDMS into the PU backbone. Thermogravimetry analysis revealed that thermal stability of the composite improves significantly with incorporation of LDH into the PU matrix. This may be accredited to the barrier effect rendered by the LDH layers. Differential scanning calorimetry study reveals that with the incorporation of LDH, glass transition temperature (Tg) of the composite increases for an optimum level of loading beyond which it remains constant.