Abstract: We explore the influence of the solvent dipole moment on cation− anion interactions and transport in 1-butyl-3-methyl-imidazolium bis- (trifluoromethylsulfonyl), [BMIM+][Tf2N−]. Free energy profiles derived from atomistic molecular dynamics (MD) simulations show a correlation of the cation− anion separation and the equilibrium depth of the potential of mean force with the dipole moment of the solvent. Correlations of the ion diffusivity with the dipole moment and the concentration of the solvent were further demonstrated by classical MD simulations. Quasi-elastic neutron scattering experiments with deuterated solvents reveal a complex picture of nanophase separation into the ionic liquid-rich and solvent-rich phases. The experiment corroborates the trend of concentration- and dipole moment-dependent enhancement of ion mobility by the solvent, as suggested by the simulations. Despite the considerable structural complexity of ionic liquid−solvent mixtures, we can rationalize and generalize the trends governing ionic transport in these complex electrolytes.