Lamellar liquid crystals (LLCs) have been shown to have lubrication properties in many documents due to their bilayer structure. Ionic liquids are often used as additive or surfactant in LLCs. However, ionic liquids used as cosurfactants, which lead to a transition from the hexagonal liquid crystals to LLCs, are relatively rare. Herein, the microstructure of Triton X-100/C(n)mimNTf(2)/H2O LLCs formed by using 1-alkyl-3-methylimidazolium bis- (trifluoromethylsulfonyl)imide ionic liquid (C(n)mimNTf(2), n = 8, 12, 16) as cosurfactant has been determined by polarized light microscopy, small angle X-ray scattering, and H-2 NMR technique, and their rheological and tribological properties were investigated. These LLCs show good friction-reducing and antiwear performances. The correlation between the microstructure of the LLCs and their lubricating mechanism is established. The increase of the concentration of C(n)mimNTf(2), and the length of alkyl chain in the LLCs can lead to an obvious reduction in friction coefficients and wear volumes, which are attributed to the higher order of amphiphilic molecules, the thickness of the amphiphilic bilayer, and the smaller cross-sectional area of the polar head group at the hydrophilic and hydrophobic interfaces. The protective film formed by the physical adsorption of ionic liquid LLCs on the surface of friction disk pair and the tribochemical reaction has effectively promoted the lubrication effect. The good lubricating property and antiwear capability indicate their promising and potential applications in water lubrication and biological lubrication.