The thermal transition, crystallization and spherulitic morphology of starch-g-poly (1,4-dioxan-2-one) copolymers were studied by means of differential scanning calorimetry (DSC) and polarized optical micrographs (PM). It is found that the graft structures of copolymers have obvious effects on the thermal and crystallization behaviors. Because there were more defect sites in the crystalline phase originating from the short grafted chains of poly (1,4-dioxan-2-one)(PPDO), the crystal structure of the copolymers was much less perfect than that of PPDO. PM revealed that the spherulitic morphology of the graft copolymers depended on graft structures and crystallization temperatures. From the single polarized micrograph of the graft copolymers it was observed clearly that the starch segments acted as nucleation sites. The Avrami equation was used to analyze the overall isothermal crystallization of the graft copolymers. Avrami exponents were almost constant at crystallization temperatures Tc ranging from 45 to 60 8C. Both the PM observation and the DSC investigation (crystallization rate constant, K values) indicated that the graft copolymers crystallize faster than pure PPDO, especially at higher crystallization temperatures.