A methodology is demonstrated for the rapid evaluation of the bulk electrolyte characteristics of the salt lithium difluoro(oxalato)borate (LiDFOB) (or lithium oxalyldifluoroborate (LiODFB)). Acetonitrile (AN) has been used as a model solvent. Utilizing information from a combination of methods-i.e., the determination of the (AN)(n)-LiDFOB thermal phase behavior (phase diagram and the corresponding solvate crystal structures), a Raman spectroscopic evaluation of the solvation/ionic association interactions and molecular dynamics (MD) simulations-detailed insight into the coordination interactions of the DFOB- anion is obtained and explanations are readily available for the solution behavior and variability in the transport properties (viscosity and ionic conductivity) of AN solutions with this salt relative to other lithium salts. (C) 2013 The Electrochemical Society. All rights reserved.