Herein we report the generation of counterion radicals and their reactions in quaternary water-in-oil microemulsion. Hydrated electrons in the microemulsion CTAB/H₂O/n-butanol/cyclohexane have a remarkably short half-life (~1 μs) and lower yield as compared to that in the pure water system. Electrons are solvated in two regions: one is the water core and other the interface; however, the electrons in the water core have a shorter half-life than those in the interface. The decay of the solvated electrons in the interface is found to be water content dependent and it has been interpreted in terms of increased interfacial fluidity with the increase in water content of the microemulsion. Interestingly another species, dibromide radical anion (Br₂^•-) in CTAB and CPB microemulsions have been observed after the electron beam irradiation. Assuming that the extinction coefficient of the radicals is the same as that in the aqueous solution, the yields of the radicals per 100 eV are 0.29 and 0.48 for the Br₂^•- radical in CTAB and CPB containing microemulsions (W0 = 40), respectively, under N2O saturated conditions. Further, we intended to study electron transfer reactions, which occur at and through the interface. The reaction of the Br₂^•- radical anion with ABTS [2,20-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)] has been studied to generate the ABTS radical in the water core, and further, its reaction has been investigated with the waterinsoluble molecule vitamin E (tocopherol) and water-soluble vitamin C (ascorbic acid). In the present study, we were able to show that, even for molecules which are completely insoluble in water, ABTS scavenging assay is possible by pulse radiolysis technique. Furthermore, these results show that it is possible to follow the reaction of the hydrated inorganic radical with solutes dissolved in the organic phase in a microemulsion without use of a phase transfer catalyst.