Our continuing research on the preparation, characterization, materials properties, and biodegradability of polylactide (PLA)/organically modified layered silicate (OMLS) nanocomposites has yielded results on PLA/montmorillonite nanocomposites. Montmorillonite (mmt) modified with dimethyldioctadecylammonium cation was used as an OMLS for nanocomposite preparation. The internal structure of nanocomposites on the nanometer scale was established with the use of wide-angle X-ray diffraction patterns and transmission electron micrographic observation. All nanocomposites exhibited significant improvement in crystallization behavior, mechanical properties, flexural properties, heat distortion temperature, and O2 gas permeability when compared with pure PLA.