The spectroscopic behavior of 6-propionyl-2-(N,N-dimethyl)aminonaphthalene (PRODAN) is investigated in different environments. ranging from homogeneous solutions of different polarities to diffuse interfaces mimicking membranes. The variety of experimental data as well as computational results present in the literature still do not clarify the nature of the emission process; in particular, it is not well-established whether fluorescence in such a molecule occurs from a planar or from a twisted intramolecular charge transfer state. The first part of the work is thus devoted to better understand how the electronic transition processes occur in homogeneous solvents. The effect of the medium polarity as well as the hydrogen bond formation are studied. In the second part of the paper, a first attempt to interpret the experimental results of PRODAN in unilamellar vesicles is carried out. The complexity of the still-open questions about the photophysics of PRODAN has prompted us to base the study on quantum-mechanical calculations performed at various levels of theory, namely, DFT, TDDFT, CIS, and SAC-CI, and to include the effects of the environment in a self-consistent way. This is achieved by using the integral equation formalism version of the polarizable continuum model (IEFPCM). lEFPCM is a quite versatile approach, being able to treat equilibrium and nonequilibrium solvation in both homogeneous and heterogeneous media.