Amphiphilic ionic liquids (ILs) based on 3-hexadecyl-1-methyl imidazolium cation, [C16mim](+), having aromatic anions, 4-hydroxybenzenesulfonate, [HBS], benzenesulfonate, [BS], and p-toluenesulfonate, [PTS], as counterions have been synthesized and investigated for their micellization behavior in aqueous medium. The surface activity of investigated ILs has been established by surface tension measurements, whereas bulk behavior has been investigated by conductivity and steady-state fluorescence measurements. The investigated ILs exhibited 2-3 fold lower critical micelle concentration (cmc) as compared to analogous ILs or conventional surfactants with nonaromatic counterions. The polarity of the cybotactic region of pyrene decreases along with decrease in extent of water penetration toward palisade layer of micelle with increase in hydrophobicity of counterion. Relatively more hydrophobic anions, i.e., [BS](-) and [PTS](-), have been found to form excimer in palisade layer of micelle, whereas [HBS](-) remains in close vicinity of imidazolium head groups of micelle as established from inherent fluorescence of aromatic anions. Isothermal titration calorimetry measurements have provided insights into thermodynamics of micelles. The strength of binding and relative position of aromatic anions in micelle has been found to affect the characteristic properties of micelle as deduced from (1)H NMR measurements. The micelles with different sizes and shapes such as spherical, partially elongated, or long rod-like micelles have been observed for different ILs depending of nature of aromatic anions as established from dynamic light scattering and transmission electron microscopy measurements.