Well-defined amphiphilic block copolymers, poly(ethylene glycol) methyl ether-b-poly(styrene) (mPEG-b-PS), in which the PS blocks had different molecular weights, were synthesized by atom transfer radical polymerization (ATRP). Through introduction of selective solvents for the blocks, crystalline and amorphous blocks were self-assembled into different micelle structures in solutions. Atomic force microscopy (AFM) was used to characterize the micelle structures. It was observed that spherical micelles were always formed, whereas lamellar aggregates appeared only in the PS-selective solvent when the molecular weight of the PS block in mPEG-b-PS was low. The crystallizable mPEG blocks were self-assembled into either the core or corona of the micelles formed. The effects of the self-assembled structures on the crystallization behavior of mPEG blocks were then investigated with differential scanning calorimeter DSC. When the PS molecular weight was much larger than that of mPEG, the result showed that the crystallinity of the mPEG block was lower when mPEG blocks crystallized in the corona than that in the core of the micelles. In this case, when mPEG blocks crystallized in micelle coronae, the micelle core formed by insoluble PS blocks was very big, so mPEG chains had to distribute sparsely in the micelle coronae. It was hard for mPEG chains in one micelle or among different micelles to gather together to crystallize. However, when the PS molecular weight was lower than that of mPEG, the crystallinity of mPEG was higher when the mPEG chains crystallized in the micelle corona, as the core formed by insoluble PS was small and the mPEG chains in the corona were easy to aggregate and crystallize. (c) 2007 Elsevier Ltd. All rights reserved.