We report an Ar/Kr ion laser induced spectrally resolved S 1 → S 0 emission from an azulene in a host naphthalene crystal observed at the helium λ-point and at 77 K. Less well resolved S 1 → S 0 emission from crystalline azulene dispersed in a KBr pellet at 300 K is also reported. For the 6471 Å excitation the emission from the azulene in naphthalene system is analyzed in terms of three components: a resonance enhanced Raman emission originating from a nonstationary laser photon energy state 800 cm −1 above the S 1 origin, a partially relaxed fluorecence originating from the 665 cm −1 vibrational level of S 1 and a totally relaxed fluorecence from the S 1 origin (14651 cm −1). The interpretation of the spectral lines is based on totally symetric vibrational modes (406, 679, 825,902, 1203, 1269, 1401, and 1586 cm −1) the most prominent of which is the progression forming 825 cm −1 mode. On the basis of both energies and intensities, correlations are made between ground and excited state vibrations and are compared with earlier results. Based on our results, a discussion is given on a plausible relaxation scheme for our system including the influence of Franck—Condon factors on the observability of unrelaxed emission.