Polystyrene/poly(ethylene oxide) diblock copolymers bearing anthracene or phenanthrene groups at the block junctions were synthesized by sequential anionic polymerization using cumyl-potassium as initiator. Labelled copolymers were characterized by means of ultraviolet (UV) spectroscopy, gel-permeation chromatography (GPC) and H-1 NMR spectroscopy. The solutions of the prepared copolymers in water and 1,2-dichloroethane/methanol mixtures were studied by fluorescence spectroscopy. The intermolecular energy transfer process confirms the presence of organized structures (micelles) in solutions.