The conformational behavior of hydrophobically modified shell-forming poly(methacrylic acid) (PMA) blocks in 1,4-dioxane–water solutions of polystyrene-block-poly(methacrylic acid) (PS-PMA) micelles was studied by a combination of several experimental methods (static and quasielastic light scattering, fluorescence techniques and atomic force microscopy). The nonradiative energy transfer (NRET) studies with fluorescently tagged samples show that the hydrophobic anthracene groups attached to the ends of PMA blocks try to avoid the aqueous medium and return closely to the PS core, forcing PMA chains to loop back. Computer modeling (Monte Carlo and mean-field calculations) was performed to get better insight into the conformational behavior. Computer studies reproduce the behavior on the semi quantitative level.