A multiblock fluorinated polyurethane was synthesized using tetraphenylethane-based polyurethane as macroiniferter to free-radically polymerize 1H,1H,3H-trihydro perfluoro-2,4-dimethylpentyl methacrylate (FDPMA). Simultaneous self-assembly occurred in FDPMA polymerization process and various nanostructures, like multicore particles, formed depending on FDPMA concentration. Fluorophobic effect and the cooperation of the fluorinated blocks with polyurethane blocks are demonstrated to be the main contribution. That soluble FDPMA in DMF becomes insoluble after polymerization triggers the self-assembly process and leads to the nanostructure formation, and the polyurethane blocks that are soluble in DMF and immiscible with the fluorinated blocks stabilize the discrete nanostructures. Further, the nanostructures in solutions can evolve into various morphologies, such as disk and fiber, when dried to solid state. All these results not only reveal the feasibility and robustness of the multiblock copolymer on the modulation of self-assembly structure but also represent a facile and efficient approach for novel nanostructure construction. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2151-2170