The microstructure of water solubilized in H2O/surfactant/n-heptane ternary systems has been investigated by employing H-1-NMR and FT-IR spectroscopic techniques. Two reverse micellar systems were prepared and studied, i.e., sodium bis(2-ethylhexyl) sulfosuccinate in n-heptane (H2O/AOT/n-heptane) and sodium bis(2-ethylhexyl) phosphate in n-heptane (H2O/NaDEHP/n-heptane). H-1-NMR data showed that the chemical shift of water protons for the AOT and NaDEHP reverse micelles varied downfield and upheld, respectively, with an increase of the water content. The opposite shift directions with increasing water content are interpreted as due to a composition change of the solubilized water associated with head-groups and sodium counterions in reverse micellar systems. On the basis of deconvolution results of FT-IR spectra, a four-component model is proposed to interpret the FT-IR and H-1-NMR results.