PScomb-block-PEOcomb copolymers having a poly(chloroethyl vinyl ether)-b-poly(hydroxy ethyl vinyl ether) backbone with polystyrene chains on one side and poly(ethylene oxide) chains on the other, i.e. (PCEVE-g-PS)-b-(POHEVE-g-PEO), were synthesized. The strategy is based on grafting of polystyryllithium onto the reactive chloro functions of the poly(chloroethyl vinyl ether) first block and on grafting polyethylene oxide from the hydroxyl functions of the second block. This procedure allows the preparation of densely grafted amphiphilic diblocklike, Janus-type, comblike copolymers with high molar masses and narrow polydispersity. The characteristics and dimensions of isolated (PCEVE-g-PS)-b-(POHEVE-g-PEO) macromolecules were studied by light scattering in THF, a good solvent of both PS and PEO branches, as well as using AFM imaging of highly diluted deposits. Unimolecular rodlike nano-objects with distinct PS and PEO domains were observed, in agreement with their diblocklike structure. In relation with their amphiphilic nature, the combs can self-assemble in different morphologies. When graphite deposits are made from more concentrated methylene dichloride solutions, the PScomb-b-PEOcomb copolymers self-assemble directly on the substrate, forming flowerlike molecular aggregates interconnected by their PEO moieties. When deposits are made from a selective solvent (methanol) of the PEO comb block, hyperbranched micelles formed in the solution retain their structure on the solid substrate, yielding well-defined spherical objects.