Aqueous Biphasic Systems (ABS), in which two aqueous phases with different compositions coexist as separate liquids, have first been reported over a century ago with polymer solutions. Recent observations of ABS forming from concentrated mixtures of inorganic salts and ionic liquids raise the fundamental question of how "different" the components of such mixtures should be for a liquid-liquid phase separation to occur. Here we show that even two monovalent salts sharing a common cation (lithium) but with different anions, namely LiCl and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), may result in the formation of ABSs over a wide range of compositions at room temperature. Using a combination of experimental techniques and molecular simulations, we analyze the coexistence diagram and the mechanism driving the phase separation, arising from the different anion sizes. The understanding and control of ABS may provide new avenues for aqueous-based battery systems.