Novel porous aminopropyllsooctyl polyhedral oligomeric silsesquioxane (POSS) modified montmorillonite clay complexes (POSS-Mts) with large interlayer distance and specific surface area have been successfully prepared via ion-exchange reaction and followed by freeze-drying treatment. The morphology of the POSS-Mts is highly influenced by the POSS concentration, pH of the suspension and drying procedure, but the interlayer distance of the POSS-Mts does not change much when the POSS concentration is above 0.4 CEC. The POSS-Mts were used as Sn-catalyst supporters to initiate the ring-opening polymerization of cyclic butylene terephthalate oligomers (CBT) for the first time. No diffraction peak was detected by wide-angle X-ray diffraction for the polymerized composites (pCBT/POSS-Mt), even at 10 wt % loading of POSS-Mt. A clay network rather than exfoliation structure was observed unexpectedly in the composites by transmission electron microscopy. The pCBT/POSS-Mt composite with 10 wt % POSS-Mt was further melt-compounded with commercial PBT resin as a master batch. The tensile properties of the resultant PBT/POSS-Mt composites were highly improved as compared to the pristine PBT due to the homogeneous dispersion of POSS-Mt in the PBT matrix.