In this work we investigate the behavior of the glycerol (GY):N,N-dimethylformamide (DMF) mixture in homogeneous and sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane reversed micelles (RMs) media. To achieve this goal we have used the solvatochromic behavior of 1-methyl-8-oxyquinolinium betaine (QB) as an absorption probe, and dynamic light scattering (DLS). QB shows strong preferential solvation when it is dissolved in the GY:DMF mixture, and, as QB is a good hydrogen bond acceptor molecular probe, it is preferentially solvated by the GY DMF hydrogen-bonded (H-bonded) species. On the other hand, when the GY:DMF mixture was investigated in AOT RMs, the results show that the mixture is encapsulated in the polar core of the AOT RMs. DLS confirms the formation of the GY:DMF/AOT/n-heptane RMs since an increase in the W(s) = ([GY] + [DMF])/[AOT] values causes an increment in the RMs droplets sizes. The solvatochromic behavior of QB, which resides at the AOT RMs interface, shows that QB is mostly solvated by GY molecules, especially at low W, values. Thus, it seems that upon encapsulation inside the polar core of the AOT RMs, the GY-DMF interaction diminishes due to the strong AOT-GY interaction. (1)H NMR chemical shifts of GY and DMF measured in the different AOT RMs investigated shows that GY and DMF behave practically as noninteracting solvents inside the RMs.