Asystematic study of electrolytes has been conducted to explore howsolution structure dictates electrolyte properties. Specifically, the transport properties (viscosity, conductivity and molar conductivity) of acetonitrile-lithium salt mixtures, (AN)(n)-LiX, are reported for electrolytes with LiPF6, LiTFSI (i.e., LiN(SO2CF3)(2)), LiClO4, LiBF4 and LiCF3CO2. These salts have widely varying ion solvation/ionic association behavior which is directly reflected in the transport properties of the AN solutions. Information about the solution structure has been utilized, in concert with molecular dynamic (MD) simulations, to provide mechanistic explanations for the variability noted in the transport properties of the electrolyte mixtures. (C) 2013 The Electrochemical Society. All rights reserved.