A Raman spectroscopic evaluation of numerous crystalline solvates with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI or LiN(SO2CF3)(2)) has been conducted over a wide temperature range. Four new crystalline solvate structures-(PHEN)(3):LiTFSI, (2,9-DMPHEN)(2):LiTFSI, (G3)(1):LiTFSI and (2,6-DMPy)(1/2):LiTFSI with phenanthroline, 2,9-dimethyl[1,10]phenanthroline, triglyme, and 2,6-dimethylpyridine, respectively-have been determined to aid in this study. The spectroscopic data have been correlated with varying modes of TFSI-center dot center dot center dot Li+ cation coordination within the solvate structures to create an electrolyte characterization tool to facilitate the Raman band deconvolution assignments for the determination of ionic association interactions within electrolytes containing LiTFSI. It is found, however, that significant difficulties may be encountered when identifying the distributions of specific forms of TFSI- anion coordination present in liquid electrolyte mixtures due to the wide range of TFSI-center dot center dot center dot Li+ cation interactions possible and the overlap of the corresponding spectroscopic data signatures.