In the Triton X-100/n-C_nH_2n+1COOH/H₂O system, n-C_nH_2n+1COOH can be used as a cosurfactant. As its chain length increases, the regions of the microemulsions showing oil-in-water (O/W), water-in-oil (W/O), and bicontinuous structures decrease and at the same time, the region of the lamellar liquid crystal increases. In the O/W region, the distribution coefficient K of n-C_nH_2n+1COOH between Triton X-100 micellar phase and water phase increases with the chain length of saturated unbranched monocarboxylic acid. The relationship between the standard solubilization Gibbs free energy of saturated unbranched monocarboxylic acid and the number of methylene groups in the saturated unbranched monocarboxylic acid is given by the equation: ΔG _m ⁰=−2.364−2.818 n(CH₂) kJ·mol⁻¹ in the Triton X-100 micellar system. In the lamellar liquid crystal region, small-angle X-ray diffraction shows that the thickness of the bilayer d ₀ is independent of the weight ratio of n-C_nH_2n+1COOH to Triton X-100, but the volume of the solvent penetrating from the solvent layer to the amphiphilic bilayer increases with the weight ratio of n-C_nH_2n+1COOH to Triton X-100. Furthermore, the d ₀ value increases with the chain length of saturated unbranched monocarboxylic acid, which will contribute to the formation and stabilization of the lamellar liquid crystal.