Ionic liquids (ILs) are salts possessing many properties that make them attractive for use in a wide range of applications including batteries. One of the biggest drawbacks of ILs is that they tend to be more viscous than conventional solvents, which means low ionic conductivity when used as electrolytes in batteries. One effective way to lower the viscosities is to mix ILs with low viscosity additives such as molecular solvents. An obvious disadvantage of mixing molecular solvents with ILs is that the extremely low volatility of the IL is compromised by the finite vapor pressure of the diluent. One strategy to overcome this is to mix ILs with molecular solvents that are themselves of very low volatility. One such class of compounds are the glymes, which are oligoethers having a CH3O-(CH2CH2O)n-CH3 structure. In addition to having low volatility, glymes are effective at dissociating salts because of the electron donating nature of their ether oxygen groups. They also tend to have high thermal and electrochemical stability, which has led many groups to investigate mixing glymes with alkali metal salts (most commonly Li+ [NTf2]) for use as electrolytes in batteries. The alkali metal cation tends to coordinate with the oxygen atoms of the glyme, which can significantly lower the melting point of the salt. Such systems usually retain the attractive properties of pure ILs but the transport properties are improved. They are considered a new class of ILs and have been termed “solvate ILs”. Tetraethylene glycol dimethyl ether (tetraglyme or G4) is a particularly promising glyme. While there are many studies devoted to the properties of Li-based solvate ILs, much less work has been done investigating the properties of mixtures containing glymes and more conventional ionic liquids. In the current work, the density and viscosity of the IL [C6mim][NTf2]) and its mixtures with tetraglyme were measured at different temperatures and concentrations. Molecular dynamics (MD) simulations were also carried out on the mixtures in order to compute the density, self-diffusivity, viscosity, ideal ionic conductivity and liquid structure. We find that both the density and viscosity drop with increasing temperature and G4 concentration. Detailed analysis of the simulation results suggests that G4 preferentially solvates the cations, thereby weakening the interactions with the anions and resulting in faster dynamics, particularly for the anions. Such behavior was previously observed in solvate ionic liquids. Based on the simulation results of a model G4 system, it was further revealed that the localized negative charges on the oxygen atoms of G4 are primarily responsible for the preferential solvation of cations. If G4 (or a similar solvent) instead had large localized positive charges, it would tend to preferentially solvate the anions, resulting in increased cation mobility. This suggests a strategy for selecting molecular solvents that will selectively enhance cation dynamics.