Mixtures of dissimilar surfactants can have superior properties compared to those of the individual surfactant components involved, which provide impetus for research on interactions between surfactants. It was also demonstrated that a change in the composition of external phase promotes remarkable changes in interfacial properties of reverse micelles (RMs), which are crucial to understand the system in order to use them as nanoreactors. Hence, it should be achievable to explore the influence of non-ionic Tween-85 on the properties of anionic AOT based micelle as well as RMs in fatty acid esters [e.g., ethyl myristate (EM), ethyl palmitate (EP) and ethyl oleate (EO)]. A comprehensive micellization behavior is studied at different mixed compositions (XTween-85) by surface tension method. Non-ideal mixing behaviors along with synergistic interaction between the constituent surfactants in the mixed micelles are evidenced. Mixed micelles illustrate favorable micellization behavior in terms of thermodynamic parameters. Further, fatty acid ester medium-based mixed RM shows synergism in water solubilization capacity. Microstructures of these systems are investigated by conductance, DLS, and FTIR studies. The solvation and rotational relaxation dynamics using picosecond time-resolved emission spectroscopy (TRES) is used to investigate the effect of XTween-85 as well as chemical architecture of fatty acid esters for the first time on the excited state dynamics of fluorophore. The solvation dynamics is found to be faster with an increase in XTween-85 and the average solvation time follows the order, EO<EP<EM, which collaborates well with …