Dye solubilization in microemulsion based on Cetyltrimethylammonium bromide (CTAB) and its modified forms (counter-anions based upon Zn, Cu and Fe) is comparatively innovative and not explored in existing literature. Here, surfactant with modified counterions (SMCs) were used to study the effects of metal chlorides (ZnCl, CuCl and FeCl) modifications on the comparative solubilization of Rhodamine-B (RB) by Cetyltrimethylammonium bromide (CTAB) and its modified forms. The solubility of RB in different microemulsions were studied using UV-Visible spectroscopy and phase diagrams of CTAB with modified counter ions CTA[ZnCl.Br] named as CZN-1, CTA[CuCl.Br] named as CCU-1 and CTA[FeCl.Br] named as CFE-1 based upon surfactant with modified counter ions (SMCs). Four different points in microemulsion region of phase diagram were selected with different percentage composition of S (surfactant and co-surfactant), oil and RB (taken as water component). The interaction of RB, CCU-1, CFE-1 and CZN-1 within microemulsion environment were studied using Fluorescence spectroscopy. Emission spectra of RB in CCU-1 and CFE-1 based microemulsion confirmed that RB formed complexes with Cu and Fe ions. It was also found that RB was less soluble in CTAB based microemulsion as compared to microemulsions based on SMCs. This novel research study will expose new path for future research work related to microemulsion.