The formation of aqueous biphasic systems (ABSs) based on aqueous ionic liquid (IL)/salt mixtures has been investigated via molecular dynamics simulations (with IL butyl-methyl-imidazolium triflate; salts NaCl, CsCl, SrCl2, and EuCl3). The analysis of ion distributions, solvation, and mutual interactions during the dynamics reveals the heterogeneity of all solutions due to ion segregation into mutually exclusive IL and salt domains, even in monophasic solutions ("ionic sociology"). Ion segregation and ABS formation are found to increase with (i) the salt content and (ii) the IL content, (iii) in the order Na+ < Sr2+ < Eu3+, and (iv) when the IL ion "polarity" is diminished, following experimental trends. The structuration of the solution is rationalized as a synergistic water transfer from the best donating ion pair (first hydration shell of hydrophobic moieties of IL ions) to the best accepting pair (Mn+ and Cl- ions, beyond their first shell). In ABSs, the IL- and salt-containing phases are linked by a well-defined "interface" that decreases in width when MCln becomes more hydrophilic and/or more concentrated. In the IL-rich phase of ABSs, the hydration of IL ions and their mutual interactions are shown to be similar to those displayed at aqueous interfaces.