Ethylene oxide-ethylene terephthalate segmented copolymers (EOET) with long PEO segment or high PET content have showed an obvious compositional heterogeneity. The EOET copolymers with compositional heterogeneity could be separated into soluble and insoluble fractions by extraction with chloroform. H-1-NMR measurements showed that the former contains much lower PET content than the average content value, and the latter is in reverse. DSC results revealed that PET segments in the latter would crystallize more easily, but in the former PEO segments exhibits more intensive melting peak. The thermogravimetric behaviors of EOET copolymers were between PEO and PET homopolymers. The EOET copolymers with serious compositional heterogeneity showed two stages of weight loss. TGA was sensitive to indicate the compositional heterogeneity in EOET copolymers. The compositional heterogeneity could impart a great influence on the shape memory behavior of EOET copolymers. The recovery curve of EOET copolymers with serious compositional heterogeneity also can exhibit two stages of deformation recovery. Generally, the component with worse memory behavior in EOET copolymer is an unfavorable factor, and the addition of EOET copolymer with better memory behavior into the blend is a favorable factor for the blend system.