An ordered multilayered adduct InP/CTAB/Clay has been synthesized via simple ion-exchange route that utilizes the electrostatic self-assembly between the exfoliated sodium montmorillonite nanoplatelets and the substituted InP/CTAB cationic polyelectrolytes. The obtained samples exhibit a high degree of structural ordering, with the interlammellar spacing of ca. 36.8 angstrom, which is well manifested by low-angle X-ray powder diffraction (LXRD) patterns. Transmission electron microscopy (TEM) images indicate its structural hierarchy, while UV-Vis and PL spectrum demonstrates the existence of InP nanocrystals. It is found that the high CEC of Na-montmorillonite and the appropriate ratio of CTAB-to-InP, as well as the presence of the InP/CTAB polyelectrolytes would have the influence oil the purity and the formation of the stable adducts InP/CTAB/Clay. This preparative method described here can be anticipated to offer a potential strategy for building the ordered stable adducts with sandwich-like structures due to its ease, reproducibility and versatility. (c) 2005 Elsevier B.V. All rights reserved.