The poly(styrene)-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) triblock copolymer PS 200 -b-P2VP 140 -b-PEO 590 , where the subscripts refer to the number average degrees of polymerization, forms spherical micelles in water, that consist of a PS core, a pH-responsive P2VP shell and a PEO corona. This triblock has been added with homo-PS before micellization in order to increase the volume fraction of the core-forming block. The length of the added homo-PS has been varied with respect to the length of the PS core-forming block: much shorter, much longer and approximately the same. The structure of the micelles has been investigated by transmission electron microscopy, static and dynamic light scattering. Homo-PS phase separates whenever its length is larger than the one of the PS core-forming chains; otherwise this phenomenon occurs beyond a critical concentration that depends on molecular weight. The addition of homo-PS has no influence on the morphology of the micelles and on the characteristic size of both the PS core and the P2VP shell, although the hydrodynamic diameter of the micelles is decreased. Substitution of styrene for homopolystyrene results in transition from a spherical to a dominant rod-like morphology.