The aggregated domains tend to stay on top of the coil blocks for small rod-to-coil block ratio. However, the submergence of the aggregative domains into the coil blocks was thermodynamically preferred for large enough rod-to-coil block ratio. Furthermore, the photophysical properties of PF-b-PPEGMA-b-PPOPS brushes were significantly varied by the solvent stimuli. Emission peaks originating from the aggregation and/or excimer formation of PF blocks were observed after methanol treatment.