Transport properties and the associated structural heterogeneity of room temperature aqueous ionic liquids and especially of super-concentrated electrolyte aqueous solutions have received increasing attention, due to their potential application in ionic battery. This paper briefly reviews the results reported mainly since 2010 about the liquid–liquid separation, aggregation of polar and apolar domains in neat RTILs, and solvent clusters and 3D networks chiefly constructed by anions in super-concentrated electrolyte solutions. At the same time, the dominating effect of desolvation process of metal ions at electrode/electrolyte interface upon the transport of metal ions is stressed. This paper also presents the current understanding of how water affects the anion–cation interaction, structural heterogeneities, the structure of primary coordination sheath of metal ions and consequently their transport properties in free water-poor electrolytes.