Segmented poly(ether-block-amide) copolymers are typically known as polyamide-based thermoplastic elastomers consisting of hard, crystallizable polyamide block and flexible, amorphous polyether block. The melting characteristics of a poly(ether-block-amide) copolymer melt-crystallized under various quiescent, isothermal conditions were calorimetrically investigated using differential scanning calorimetry (DSC). For such crystallized copolymer samples, their crystalline structures under ambient condition and the structural evolutions upon heating from ambient to complete melting were characterized using ambient and variable-temperature wide-angle X-ray diffractometry (WARD), respectively. It was observed that dependent of specific crystallization conditions, the copolymer samples exhibited one, two, or three melting endotherms. The ambient WARD results indicated that all melt-crystallized copolymer samples only exhibited gamma-form crystals associated with the hexagonal habits of the polyamide homopolymer, whereas variable-temperature WARD data suggested that upon heating from ambient, a melt-crystallized copolymer might exhibit so-called Brill transition before complete melting. Based on various DSC and variable-temperature WAXD experimental results obtained in this study, the applicability of different melting mechanisms that might be responsible for multiple melting characteristics of various crystallized PEBA copolymer samples were discussed. It was postulated that the low (T-m1) endotherm was primarily because of the disruption of less thermally stable, short-range ordered structure of amorphous polyamide segments of the copolymer, which was only formed after the completion of primary crystallization via so-called annealing effects. The intermediate (T-m2) and high (T-m3) endotherms were attributed to the melting of primary crystals within polyamide crystalline microdomains of the copolymer. The appearance of these two melting endotherms might be somehow complicated by thermally induced Brill transition. (C) 2008 Wiley Periodicals, Inc.