This paper reports on the spectral dynamics of perylene orange in thin sol-gel films. The studies are performed at the single molecule level to retrieve local information on such samples. The fluorescence spectrum of a molecule depends on the properties of the molecule itself and especially on its conformation in the ground state and in the state reached after excitation. Studies have been performed at room temperature and at a lower temperature, around 173 K. A large number of the recorded spectra reflect dual fluorescence. It is the rule at room temperature. However, at low temperature, single molecules either are relatively free to change conformation or are caught in a rigid environment. In the latter case, they present the spectrum of a rigid dye and we have identified the signature of several conformers of perylene orange in the ground state.