The interfacial composition of the stable water/C12-S-C-12 center dot 2Br/n-hexanol/n-heptane microemulsions has been studied in detail by dilution method. The results showed a marked maximum amount of the n-hexanol populating on the surfaces of droplets (represented as a = n(a)(i)/n(s), where n(a)(i) and n(s) are respectively the moles of n-hexanol and gemini surfactant on the surface of droplets) with increasing water content. At a constant level of water addition (the molar ratio of water to surfactant W-0 = 20), a decreased with increasing the spacer length in the C-12-s-C-12 center dot 2Br molecule. The structural parameters of a w/o microemulsion were also estimated by analyzing the data of dilution experiments, and we found that the radius of the water pool was very sensitive to the increment of water content. The radius of the water pool varied from 0.74 to 5.35 nm with increasing W-0 from 10 to 50. The variation extent reached 4.61 nm. In the cases of water/CPC/n-butanol/isopropyl myristate and water/CTAB/n-butanol/isopropyl myristate, however, the corresponding variation extents were only 1.22 and 1.68 nm, respectively, when increasing comparable water content. The ratio of N ($) over bar (a)/N ($) over bar (2c) where N ($) over bar (a) and N ($) over bar (2c) are respectively the average numbers of n-hexanol and the total average numbers of alkyl chains of gemini surfactant populating on per droplet surface, decreased obviously with increasing water content at W-0 > 15. This indicated that C-12-2-C-12 center dot 2Br favored to form large droplets that were suitable to solubilize more water.