A sustainable growth of the world population entails advanced energy storage technologies. In the last decades, many different energy storage technologies have been discovered and industrialized. While all commercial technologies rely on electrochemical reduction and oxidation of metals, the use of lithium has become the number one choice in batteries due to its high energy density. Even though lithium-ion technology has more than 10 years of commercialization, the charge density of current lithium-ion batteries is far from the theoretical limit. Currently, most technological and scientific efforts have been focused on the electrodes and little attention has been paid to the electrolyte. In particular, structure property relations of the electrolyte have not been derived because simple fundamental questions about the lithium ion solvation shell structure and composition have yet to be answered. Here, we present a study of lithium hexafluorophosphate salt (LiPF₆) in pure carbonate solvents at commercial battery concentrations (i.e., 1 M). For this purpose, we used a combination of linear infrared (FTIR) and two-dimensional infrared (2DIR) spectroscopies supported with density functional theory (DFT) calculations. Our infrared experiments show the presence of two infrared bands in the carbonyl stretching region which are assigned to the lithium-coordinated and free carbonyl stretches. The 2DIR spectra of LiPF₆ in either linear or cyclic carbonate solvents show the presence of a cross peak between the “free” and “coordinated” carbonyl stretches indicating a tetrahedral arrangement of linear carbonate molecules in the lithium solvation shell. Notably, 2DIR spectra also demonstrate that the lithium ion solvation shell is not a perfect tetrahedron. Ab-initio calculations confirm our assignments of the infrared bands. The 2DIR experiments also reveal that linear and cyclic carbonates have very different dynamics where the cyclic carbonates presents a much more ordered structure than its linear counterpart even as a pure solvent. Finally, our experiments demonstrate that simple structural modifications in the carbonates impact significantly the microscopic interactions of the system as seen from the formation of distinct ion pairs in the two carbonates. In summary, the contrasting differences observed in the structure, motions, and composition of the lithium ion solvation shell for the cyclic and the linear carbonates show new molecular information about carbonate-based lithium ion electrolytes.