The microstructural characteristics of primary amine N1923/n-heptane/alcohol/water reverse micelles have been investigated by means of the dilution method and FT-IR spectroscopic and TEM techniques. Some structural parameters have been obtained. The broad bands obtained for water, alcohol, and primary amine N1923 bands have been resolved by both Gaussian and Lorentzian curve-fitting programs, and the vibrational characteristics, particularly the peak area and relative content corresponding to each peak, have been analyzed and assigned. It has been observed that the aqueous core of the reverse micelle droplet is composed of bound water and bulk water while a little free water remains at the interface. The hydration number of RNH3+ increases with the addition of water; however, it almost remains a constant under the conditions of various alcohols with the same content of water. All that has been obtained is very significant for the study of the mechanism of amine extraction systems.