An exfoliated nanocomposite was prepared by the film-casting technique from C25A organo-modified clay and a new biodegradable polyester derived from glycolic acid and 6-hydroxyhexanonoic acid. This polyester has a sequential monomer distribution and high crystallinity, allowing a detailed study of its isothermal crystallization. The influence of the clay on the crystallization behavior was investigated by optical microscopy, simultaneous SAXS/WAXD synchrotron radiation and FTIR spectroscopy. Primary nucleation and crystal growth rate decreased significantly with the incorporation of nanoparticles. In addition, the overall crystallization rate of the nanocomposite was logically lower than that of the neat polyester. Bulk crystallizations were modeled from FTIR data with the Avrami equation. The results showed spherulite growth geometry and predetermined (heterogeneous) nucleation for both samples. Morphological studies revealed that both the crystal and the amorphous layer thicknesses were influenced by the presence of silicate layers. The overall percentage of crystallinity and the size of crystalline domains decreased with the addition of the highly miscible organoclay. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 33-46, 2010