We demonstrate here that equilibria of electrolytes between a water phase and an (organic) solvent phase containing amphiphilic extractants depend not only on complexation toward nearest neighbors but also on long range supramolecular interactions (LRI). Taking into account bulk, polarization and chain reorganization terms, we show that the net free energy difference associated with one metal ion transfer from water results from a strong inhibition (>25 kBT/ metal ion) due to colloidal long range interactions competing with differences in complexation considered in surpramolecular chemistry (≈−30 kBT/ metal ion). LRI also influence selectivity.