Liquid structures of the bis(trifluoromethanesulfonyl)amide based ionic liquids composed of 1-ethyl-3-methylimidazolium and N-methyl-N-propylpyrrolidinium [(C(2)mIm(+)][TFSA(-)] and [C(3)mPyrro(+)][TFSA(-)], respectively) and Li+ ion solvation structure in their lithium salt solutions were studied by means of high-energy X-ray diffraction (HEXRD) technique with the aid of MD simulations. With regard to neat ionic liquids, a small but significant difference was found at around 3.5 angstrom in the intermolecular radial distribution functions G(inter)(r)s for these two ionic liquids; i.e., G(inter)(r) for [C(2)mIm(+)][TFSA(-)] was positioned at a slightly shorter region relative to that for [C(3)mPyrro(+)] [TFSA(-)], which suggests that the nearest neighboring cation anion interaction in the imidazolium ionic liquid is slightly greater than that in the other. With regard to Li+ ion solvation structure, G(inter)(r)s for [C(2)mIm(+)][TFSA(-)] dissolving Li+ ion exhibited additional small peak of about 1.9 angstrom attributable to the Li+-O (TFSA(-)) atom atom correlation, though the corresponding peak was unclear in [C(3)mPyrro(+)][TFSA(-)] due to overlapping with the intramolecular atom atom correlations in [C(3)mPyrro(+)]. In addition, the long-range density fluctuation observed in the neat ionic liquids diminished with the increase of Li+ ion concentration for both ionic liquid solutions. These observations indicate that the large scale Li+ ion solvated dusters are formed in the TFSA based ionic liquids, and well support the formation of [Li(TFSA)(2)](+) cluster clarified by previous Raman spectroscopic studies. MD simulations qualitatively agree with the experimental facts, by which the decrease in the long-range oscillation amplitude of r(2){G(r) - 1} for the Li+ containing ionic liquids can be ascribed to the variation in the long-range anion anion correlations caused by the formation of the Li+ ion solvated dusters.