AbstractA series of new dialkyl imidazolium based ILs viz. N‐butyl‐N‐alkylimidazolium bromides, [CmCnmim][Br], where m=4, n=4, 8 and 12 have been synthesized, characterized and investigated for their self‐aggregation behavior in aqueous medium. Various techniques such as tensiometry, steady state fluorescence, isothermal titration calorimetry (ITC), dynamic light scattering (DLS), transmission electron microscopy (TEM) and 1H nuclear magnetic resonance (NMR) have been employed to get detailed information about the self‐aggregation phenomenon. The investigated ILs have shown better adsorption and micellization behavior in comparison to single chain imidazolium based ILs in terms of higher adsorption efficiency and lower cmc values. TEM measurements provided insights into morphology of aggregates where spherical micelles and doughnut shaped vesicle like structures have been observed depending on the molecular structure of IL. The structure of aggregates formed by these ILs at molecular level has been proposed by analyzing the change in chemical shifts of various protons of ILs upon micellization along with information obtained from other techniques.