Chromophore-containing dendritic structures (G1, G2) are utilized to intercalate layered silicates, which results in a large d-spacing up to 126 angstrom An exfoliated morphology is obtained by mixing the dendritic structure intercalated layered silicates with polyimide in N,N-dimethylacetamide solution. The dendritic structures attached on the clay template would arrange in a non-centrosymmetric manner. This self-assembled arrangement brought about the electro-optical coefficients of 5-6 pm.V-1 for these relatively low chromophore-containing organic/inorganic nanocomposites without resorting to poling. Excellent temporal stability (100 degrees C) is also achieved.