The synthesis of luminescent rod-coil diblock and coil-rod-coil triblock copolymers containing oligo(p-phenyleneethynylene) as the rodlike block and polystyrene as the coil was achieved via atom transfer radical polymerization using oligo(p-phenyleneethynylene)s as the initiators substituted with 2-halogenopropionyloxy or 4-(bromomethyl)benzyloxy groups.