The excited-state proton transfer (ESPT) rate of photo-acids in a confined medium depends on several physical parameters of the immediate environment. We introduce a new parameter in the form of charge type at the interface of reverse micellar (RM) systems to modulate the ESPT rate. We investigate the ESPT reaction of d-luciferin in mixed RM systems composed of nonionic polyoxyethylene(5)nonylphenylether (Igepal CO-520) with cationic didodecyldimethylammonium bromide (DDAB) and anionic sodium bis(2-ethylhexyl)sulfosuccinate (AOT) in cyclohexane (Cy) at different mole fractions of Ig (XIg) and fixed hydration. ESPT is feeble in AOT RM, whereas it is favorable in the other two RMs. Addition of Ig is observed to facilitate ESPT in AOT RM linearly, whereas in DDAB, it shows a synergistic effect. The various physical parameters of water in the mixed RM water pool have been investigated using dynamic …