Diblock copolymers are known to self-organize in ordered domains. The morphology of this microphase separation depends essentially on the relative amount of each immiscible block in the copolymer (e.g. spherical, cylindrical, gyroidal and lamellar phases). The lamellar nanoscopic structures can serve as templates for the selective incorporation of inorganic nanoparticles , , for instance to get nanopatterned surfaces or for new applications such as wave guides. , In most of the studies concerning diblock copolymer self-assembly in lamellar periodic structures, diblock copolymers were synthesized by anionic polymerization which is a suitable technique to prepare well-defined high molar mass diblock copolymers. , In the present study, our aim is the synthesis of high molar mass poly(n-butyl methacrylate)-b-polystyrene diblock copolymers by Atom Transfer Radical Polymerization (ATRP). Compared to anionic polymerization, controlled radical polymerization (CRP) is a more versatile technique which requires less drastic experimental conditions. Our results highlight the self-assembly of the symmetric poly(n-butyl methacrylate)-b-poly(styrene) diblock copolymer synthesized by ATRP into a lamellar ordered structure after an annealing treatment.