Layered double hydroxides/polyimide (LDHs/PI) nanocomposites were prepared from solution of polyamic acid (polyimide precursor) and LDH-amino benzoate using N,N-dimethylacetamide as a solvent. LDH-amino benzoate (LDH-AB) was obtained by coprecipitation method. The amino benzoate, grafted on the surface of the Mg/Al nanolayers, as a connector improved the compatibility between the inorganic Mg/Al nanolayers and the organic polyimide molecules. The dispersion behavior of Mg/Al nanolayers was investigated by transmission electron microscopy and X-ray diffraction, indicating that the Mg/Al nanolayers were exfoliated in PI matrix to form LDHAB/PI nanocomposites, The maximum tensile strength and elongation of the LDH-AB/PI nanocomposites were found with the LDH-AB content of 5 and 4 wt%; respectively. The initial tensile modulus of these nanocomposites was increased with the LDH-AB content. These nanocomposites exhibited higher storage and loss moduli compared to those of pure PI. T, of these nanocomposites increased with the LDH-AB content: Coefficients of thermal expansion (CTE, below and above T-g) of these nanocomposites deceased with the LDH-AB content. The thermal properties of these nanocomposites were enhanced by the incorporation of Mg/Al nanolayers in PI matrix.