The synthesis and characterization of well-defined poly((styrene-alt-diphenylethylene)-bisoprene) diblock copolymers via sequential anionic polymerization are discussed. Indeed, modified 1,1-diphenylethylene commodity elastomers have appeared recently as an alternative to the well-known elastomers for high-temperature applications. The obtained materials were used for the preparation of block copolymer micelles. The hydrodynamic radius of the micelles in solution was determined by dynamic light scattering and the size of the core by atomic force microscopy at dry conditions. It was found that the observed characteristics of the studied micelles correlate to theoretical scaling predictions. Moreover, the average size of the unimers could be determined with high precision from the obtained experimental data and theoretical knowledge.