Modified laponites and synthetic saponites are used as precursors for the preparation of poly(epsilon-caprolactone) (PCL)/clay nanocomposites. The structure and dynamics of species intercalated in the modified clays and the corresponding nanocomposites are characterized by X-ray diffraction and magic-angle spinning NMR. The influence of the headgroup, the hydrocarbon chain length, and the loading of the surfactant on the nanocomposite formation are discussed. The yield of PCL intercalation is related to the probability of direct polymer-clay interactions and to the size of the clay platelets. Relaxation times in the laboratory and rotating frames that allow characterization of fast and slow molecular dynamics in these systems are discussed, showing a motional hetereogeneity of the intercalated species.