The formation of polymer-cyclodextrin inclusion compounds of polycarbonate (PC), poly(methylmethacrylate) (PMMA) and poly(vinylacetate) (PVAc) guests with host gamma-cyclodextrin (gamma-CD) have been successfully achieved. Coalesced bulk polymer samples were obtained by removal of gamma-CD from their inclusion compounds (ICs). The chemical and crystalline structures of ICs and coalesced PC, PMMA and PVAc were studied by Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (WAXD). The thermal transitions, thermal stability, and degradation mechanisms of the samples were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and direct insertion probe pyrolysis mass spectrometry (DIP-MS). FTIR findings indicated that the chain conformations of the bulk polymers were altered when they were included inside the CD channels and extended chain conformations were retained when coalesced from their ICs. Significant improvements were observed in the thermal transitions observed for the coalesced polymers, with glass transitions shifted to higher temperatures. The TGA results reveal that the thermal stabilities of coalesced polymers increased slightly compared to the corresponding as-received polymers. The DIP-MS observations indicated that the thermal stability and degradation products of the polymers are affected once the polymers chains are included inside the gamma-CD-IC cavities. (c) 2005 Elsevier Ltd. All rights reserved.