Noninvasive techniques such as FT-IR and H-1 NMR spectroscopy have been employed to investigate the solubilization of formamide, FA, and its aqueous solution, FA-water, by sodium 1,4-bis(2-ethylhexyl)-sulfosuccinate, AOT, in heptane or isooctane reverse micelles, respectively. Partially deuterated FA (FADH) was used in the FT-IR experiments and v(OD), n(ND) were analyzed. Also, the v(C=O) band of FA was investigated. For AOT, the changes of the SO3-group's symmetric, vs, and asymmetric, v(a), bands were also studied. The results are showing that FA is interacting strongly with the Na+ counterions of the surfactant through electrostatic interactions maintaining their hydrogen bond network present in the FA bulk. Accordingly, partially deuterated FA is "frozen" inside the aggregates and it is possible to detect, by FT-IR technique, the cis and trans isomers. Curve fitting of the v(OD) (in the FA-water mixture) band requires use of two peaks because the band is asymmetric, not because the solubilizate molecules are present in layers of different structure. The chemical shifts of the H-1 bound to N and C of FA were studied by 1H NMR. The comparison of the chemical shift of ACT in reverse micelles with FA and the FA-water mixture in the polar core of the aggregate shows that there is a strong preferential solvation of Na+ by FA (through electrostatic interaction) and the AOT's sulfonate group by water (through hydrogen bond interaction).