Thermal properties of copolyetherester/silica nanocomposites were examined by using DSC and TGA. The segmented block copolyetheresters with various hard segment structures and hard segment contents (HSC) were synthesized and their silica nanocomposite films were prepared by solution casting method. The nano-sized fumed silica particles were found to act as a nucleating agent of the copolyetheresters. The nanocomposites always showed reduced degree of supercooling or faster crystallization than the corresponding copolyetheresters. The nanocomposites also showed increased hard segment crystallinity except HSC 35 sample which had short hard segment length. In case of 2GT [poly(ethylene terephthalate)] copolyetheresters, which were not developed commercially because of their low crystallization rate, the hard segment crystallinity increased considerably. The copolyetherester/silica nanocomposites showed better thermal stability than copolyetheresters.