Supercritical carbon dioxide (scCO 2) intercalation of polycaprolactone (PCL) in layered silicates (clay) is studied. Wide angle X-ray diffraction patterns find that PCL is slightly intercalated in unmodified montmorillonite clay (NaMMT) but considerably intercalated in organic-modified montmorillonite clay (OMMT). The interlayer spacing in OMMT increases considerably from 1.94 nm in OMMT to 3.58 nm in the OMMT/PCL 10/90 sample. PCL8 having molecular weight of 80,000 is harder to intercalate into OMMT than PCL1 having molecular weight of 10,000. Higher scCO 2 pressures at a temperature allow larger intercalations of PCL in OMMT to exhibit larger interlayer spacings in OMMT. The interlayer spacings in OMMT, however, are not clearly found to relate with the CO 2 temperature at a given pressure. TGA data show that OMMT enhances the thermal stability of PCL1, with a higher content of OMMT giving a higher amount of PCL1 residue. DSC data find that the PCL1-intercalated OMMT expedites the melt-crystallization rate of PCL1 from the melt but suppresses the crystallinity of PCL1. Study of Avrami's rate constants k and exponent n finds that the PCL1-intercalated OMMT enhances the isothermal crystallization rate of PCL1 and that the crystal growth dimension is 3 for pure PCL1 but decreases with increasing OMMT content in the blends. Modulus data find that the PCL1-intercalated OMMT is an effective reinforcement for PCL8.