This investigation reported the preparation of fluorinated and nonamphiphilic well-defined poly(styrene)-block-poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate) (PS-b-PHFBMA) diblock copolymers via atom transfer radical polymerization (ATRP). Their chemical composition, structure, and bulk morphology were thoroughly investigated. In addition, their self-assembly behavior in a dilute organic mixture solution was investigated. It was found that that the ATRP could be used to prepare the well-defined fluorinated and nonamphiphilic PS-b-PHFBMA diblock copolymers in a controlled manner. The results also showed that abundant morphologies including sphere, worm-like structure, and vesicle could be formed with different volume ratios of these two solvents, which proves that the nonamphiphilic fluorinated diblock copolymers can self-assemble in a dilute solution, and the aforementioned reason for self-assembly was also discussed preliminarily in this work. Finally, the effect of temperature on the aggregates was investigated to verify whether the self-assembly behavior was to some extent temperature sensitive. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 3647-3657, 2011