The self-assembly behavior of an imidazolium-based catanionic surfactant, 1-butyl-3-methylimidazolium dodecylsulfate ([C(4)mim]-[C12H25SO4]), was investigated in water-ethylammonium nitrate (EAN) mixed solvents with different volume ratios. It is particular interesting that this simple surfactant could not only form lyotropic liquid crystals (LLC) with multimesophases, i.e., normal hexagonal (H-1), lamellar liquid crystal (L-a), and reverse bicontinuous cubic phase (V-2), in the water-rich environment but also act as an efficient low-molecular-weight gelator (LMWG) which gelated EAN-abundant binary media in a broad ! concentration range. The peculiar nanodisk cluster morphology of gels composed of similar bilayer units was first observed. FT-IR spectra and density functional theory (DFT) calculations reveal that strong H bonding and electrostatic interactions between EAN and the headgroups of [C(4)mim][C12H25SO4] are primarily responsible for gelation. The self-assembled gels displayed excellent mechanical strength and a thermoreversible sol-gel transition. It is for the first time that a rich variety of controllable ordered aggregates could be observed only by simply modulating the concentration of a single imidazolium-based catanionic surfactant or the ratio of mixed solvents. This environmentally friendly system is expected to have broad applications in various fields, such as materials science, drug delivery systems, and supramolecular chemistry.