In Figure  1, we show the radial distribution functions (RDFs) for Na–O E and Na–O A atom pairs (where O E and O A denote the oxygen atom from the solvent molecule or the anion, respectively), calculated for systems with a Na/O E ratio equal to 1:6. The plot for the ratio 1:20 is available in  Supporting Information (Figure S1). The position of the Na–O E RDF maximum does not depend much on the anion, solvent molecule, or salt concentration, and in all systems, it is located at 2.36–2.37 Å. Its height in the electrolytes based on NaFSI is larger than that for the systems with NaTFSI. Conversely, the distance at which the maximum of Na–O A RDF appears depends on the anion. For FSI anions, the position of the maximum is 2.36–2.37 Å, that is, at the same distance as for cation–ether oxygen. Distances to TFSI anions are shorter, and the Na–O TFSI maximum is located at 2.3 Å. Na–O FSI RDF values at maximum are significantly smaller than those obtained for Na–O TFSI, especially for the systems with mono- or tetraglyme at low salt concentrations. The difference in the height of RDF maxima suggests that Na + complexation by the FSI anions is weaker, especially in the solutions with short glymes as a solvent.