Dual fluorescence in N,N-Diethyl-4-nitrosoaniline (DENA) has been studied employing absorption, excitation and emission spectroscopic techniques and computational methods. The absorption and fluorescence spectra of DENA were measured in solvents of various polarities at room temperature. The emission spectra of DENA were found to exhibit a single emission band in non polar solvent (cyclohexane) and in a highly polar solvent (acetonitrile). In the contrary, two emission bands were observed in medium polar solvents (tetrahydrofuran, 1,2-dichloroethane and dichloromethane) whereby the short (local excited; LE) and long (charge transfer; CT) emission maxima correspond to the emission maxima of the compound observed in cyclohexane and acetonitrile solutions, respectively. Moreover, the two emission bands have shown strong excitation wavelength dependence, and area normalization resulted in an iso-emissive point. The two emission maxima were in addition found to correspond to two excitation maxima in 3D fluorescence spectra. Further, two minima were obtained in potential energy surface calculation of DENA. From the experimental and computational results it was concluded that the dual fluorescence may be attributed to the presence of two different ground state structural conformers of DENA in equilibrium that are stabilized through solute-solvent interaction.