Diffusion coefficients and mobilities of the ionic species of lithium electrolytes were measured using the electric field applying pulsed gradient spin-echo NMR technique. Analyses of the dynamic values showed that the lithium ion electrolyte was coordinated by four bis(trifluoromethylsulfonyl)amide anions (TFSI⁻s) and formed a cluster structure as Li(TFSI)₄³⁻in an equilibrium state. The electrolyte is lithium bis(trifluoromethylsulfonyl)amide dissolved in ionic liquid, 1-ethyl-3-methylimidazolium (EMI) bis(trifluoromethylsulfonyl)amide. High mobility was observed only when the electric field larger than a certain strength was applied to the electrolyte. This indicates that the ions are orientated in response to the electric field and the orientation may be due to the dielectric polarization of the ions. High mobility reveals the formation of pathways for efficient ion migration by the aligned ions. These results lead to the systematic designing of electrolyte materials applicable to the lithium secondary batteries with high charge rate.