The synthesis of luminescent rod−coil diblock and coil−rod−coil triblock copolymerscontaining oligo(p-phenyleneethynylene) as the rodlike block and polystyrene as the coil was achievedvia atom transfer radical polymerization using oligo(p-phenyleneethynylene)s as the initiators substitutedwith 2-halogenopropionyloxy or 4-(bromomethyl)benzyloxy groups.