Aggregation behavior and interaction of sodium dodecyl sulfate (SDS), tetradecyl trimethyl ammonium bromide (TTAB) and their mixtures with an excess of anionic surfactant in the presence of imidazolium-based ionic liquid, 1-ethyl-3-methylimidazolium bromide (EMIm Br) were investigated using surface tension, electrical conductivity, dynamic light scattering (DLS), transmission electron microscopy (TEM) and cyclic voltammetry measurements. Different physicochemical properties such as critical micelle concentration (CMC), degree of counterion dissociation (αdiss), interfacial properties, the standard Gibbs energy of adsorption and the size of aggregates were determined. The effects of ionic liquid (IL) as additive on the interactions between the surfactants; TTAB, SDS and their mixtures were analyzed on the basis of regular solution theory, both for mixed monolayers at the air/liquid interface (βδ) and for mixed micelles (βM). Interaction parameter values suggested that the formation of aggregates is due to the synergistic interactions in the case of SDS/TTAB systems and becomes more affected by adding IL. It was shown that an excess of cationic surfactant and IL resulted in an increase in the nano-aggregate sizes. The synergism observed for three component systems (surfactant–water–IL) revealed the effect of attractive electrostatic interaction, formation of a three-dimensional hydrogen bond network and hydrophobic forces on mixed micelle formation.