Six well defined PS-b-PB(1,2) diblock copolymers (PS: polystyrene and PB: polybutadiene) with almost 100% of 1,2 microstructure for the PB segment were synthesized. Size exclusion chromatography (SEC), membrane osmometry (MO) and proton nuclear magnetic resonance spectroscopy ((1)H NMR) were used for verification of the molecular characteristics and the 100% -1,2 addition for the PB blocks. Modification with heptanoyl or pentadecafluorooctanoyl chloride was accomplished via hydroboration and subsequent oxidation, leading to hydroxylated PB blocks and was verified with (1)H NMR and Fourier transform infrared (FTIR) spectroscopy. Only two samples were modified with both organic acid chloride derivatives. Structural characterization was accomplished via transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) in all cases. The self-assembly was more evident in the modified copolymers with the corresponding halides due to the increase of the molecular weight of the modified PB block. Taking into consideration the chi N values in each case and comparing the results with those of PS-b-PI copolymers already reported in the literature the discrepancies with the theoretical predictions are very small or minimal. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4292-4305, 2011