An ionic liquid (IL) 1-allyl-3-(2-methoxyethyl)imidazolium bis(trifluoromethylsulfonyl)imide ([AMO][TFSI]) is prepared, and the effect of the addition of LiTFSI into [AMO][TFSI] on the transport and physicochemical properties is studied herein. The diffusion coefficients of 1 H, 7 Li, and 19 F are determined using pulsed-gradient spin-echo NMR to study the dynamics of all ion species. The neat [AMO][TFSI] and LiTFSI-doped [AMO][TFSI] give approximately straight lines for the relationship of D vs T• -1 , demonstrating that the Stokes-Einstein equation holds for the ionic diffusivity in the binary system. NMR T 1 relation time measurements show the 1 H-T 1 and 19 F-T 1 of LiTFSI-doped [AMO][TFSI] decrease with the increase of Li salt concentration, which is due to the viscosity increases and the formation of stable coordination adducts of Li and TFSI when the salt concentration increases. From the study of chemical shift in one-dimensional NMR spectroscopy, an upfield shift in 1 H and 19 F spectra is observed in ILs with increasing lithium salt concentration; the formation of ion clusters is the dominant effect after the addition of LiTFSI in [AMO][TFSI].