The synthesis of Janus like comb copolymers constituted of polystyrene and poly(methyl vinyl ether) branches attached to a diblock backbone has been achieved using living/controlled cationic and anionic building steps associated to grafting from and grafting onto coupling processes. These comb-b-comb structures behave as isolated objects in good solvents as well as when deposited on an appropriate substrate from a good solvent. In contrast, thanks to their amphiphilic Janus-like structure, they behave like linear diblock copolymers when placed in a selective solvent of one of the comb moieties, forming stable large spherical super-micelles that could be observed on mica support. (C) 2009 Elsevier Ltd. All rights reserved.