The water/sodium bis(2-ethylhexyl) phosphate (NaDEHP) reverse micelle (RM) system is revisited by using, for the first time, molecular probes to investigate interface properties. The solvatochromic behavior of 1-methyl-8-oxyquinolinium betaine (QB) and 6-propionyl-2-(N,N-dimethyl)aminonaphthalene (PRODAN) in the water/NaDEHP/toluene system is studied, and the results are compared with those obtained in water/sodium 1,4-bis(2-ethylhexyl) sulfosuccinate (AOT)/toluene RM media. The results demonstrate that the micropolarity, microviscosity, interfacial water structure, molecular probe partition, and intramolecular electron-transfer processes are dramatically altered for NaDEHP RM interfaces in comparison to the AOT systems. Because of organic nonpolar solvent penetration into the interface, NaDEHP RM media offer an interface with lower micropolarity and microviscosity than AOT media. Also, the interfacial water in the NaDEHP system shows enhanced water–water hydrogen-bond interaction in comparison with bulk water. The AOT RM interface represents a unique environment for PRODAN to undergo dual emission.