A novel strategy to control the formation of amphiphilic brushes from metallo-supramolecular block copolymers is described. The investigated copolymer consists of a polystyrene block linked to a poly(ethylene oxide) one via a charged bis-terpyridine ruthenium(II) complex (PS-[Ru]-PEO). The initial hexafluorophosphate counterions associated to the complex have been exchanged for poly(styrenesulfonate) anions (PSS). In DMF, flexible amphiphilic brushes are observed in which PS-[Ru]-PEO chains decorate the PSS main-chain. These structures have been further transferred into pure water, resulting in the collapse of the PS chains into hydrophobic cores. Spherical or worm-like micelles have been observed in water, depending on the length of the PSS chain.