The studies concluded that the chelate effect has to be considered as another important criterion for distinguishing between concentrated solutions and SILs. In 2011, Yoshida et al. studied [Li][NTf 2 ]/G3 and [Li][NTf 2 ]/G4 over a wide concentration range and investigated the thermal and transport properties of the binary mixtures at 303 K. They found identical values for the self-diffusion coefficients of G3 and lithium cations for the equimolar mixtures, suggesting the formation of long-lived complex cations for this composition. Following this, several experimental studies investigated the electrochemical and transport behavior of the equimolar mixtures of [Li][NTf 2 ] and G3 or G4 supporting the findings, further proving the (oxidative) stability of the cationic complexes and exploring their potential for usage as battery electrolytes. SILs formed by equimolar mixtures of [Li][NTf 2 ] with G3 or G4 have also been extensively studied by theoretical methods. An early study by Diddens et al. laid the foundation for understanding their solvation structure and ion transport mechanisms. In 2014, Tsuzuki and co-workers [10] were the first to clarify the molecular structure of the equimolar mixture of [Li][NTf 2 ] and G4 at 300 K, reporting Li-O coordination numbers of up to 5, which was later confirmed by other studies. In 2018, Sun and Hamada 35 investigated a mixture with low salt concentration as well and concluded that a two-fold glyme-coordinated state ([Li(G4) 2 ] + ) is preferred here, whereas the one-fold glymecoordinated structure ([Li(G4) 1 ] + ) dominates in the equimolar composition. Later, in 2020, Thum et al. also confirmed the crown-etherlike [Li(glyme) 1 ] + complexes for equimolar mixtures with both G3 and G4 at ambient conditions. Eyckens et al. characterized the solvent properties and polarity of G3 and G4 SILs concluding high polarity and significant electron pair accepting characteristics, with relatively low hydrogen bond accepting abilities, primarily due to the influence of the [NTf 2 ] - anion. Dong et al. investigated mixtures of [Li][NTf 2 ] and G4 concerning ion transport mechanisms, demonstrating that [Li] + transport in these SILs is significantly reduced due to strong [Li] + -glyme interactions leading to longlived complexes and anti-correlated ion motion. The authors suggest that medium-sized glymes (e.g., G2 or G3) provide a better balance between ion transport and other desirable properties like thermal stability and electrochemical stability. Recent studies further support and refine these insights. However, so far, only a few studies have focused on the full concentration range of the lithium salt in the glyme solvents. Kitada et al. report that adding [Li][NTf 2 ] to an equimolar mixture of the lithium salt and glyme solvent changes the electrochemical properties drastically. Here, we present, to the best of our knowledge, the first systematical molecular dynamics (MD) simulation study on G3-based SILs, investigating both, the temperature dependence and the composition dependence of the structure of the complexes formed in mixtures of lithium salts and G3 with implications for the transport properties of these systems. We recently determined the competition between cation-anion and cation-G3 interactions in SILs by far-infrared and mid-infrared spectroscopy, providing experimental evidence for the existence of different coordination states of [Li] + cations in SILs depending on the composition of the mixture. Expanding on this mostly experimental study, we focus here on the same binary system, characterizing the solvation structure of the investigated systems in detail, shedding light on their typical coordination patterns, and understanding their temperature behavior. We demonstrate that the observed structural changes and solvation patterns have a profound impact on technologically important transport properties of these model electrolyte systems, such as diffusion, viscosity, and ionic conductivity.