A weak fluorescence from the S-2(pi,pi*) state of thiocoumarin in perfluorohydrocarbons and n-hexane solutions, of a quantum yield similar to 6.5 x 10(-5), and similarly weak phosphorescence from the T-1(pi,pi*) state, at room temperature, were measured. A distinct dependence of the shape and position of the fluorescence band on the energy of vibrational excitation within the S-2(pi,pi*) state was found and interpreted as a result of emission from the unrelaxed vibrational levels. The lifetime of the S-2 State was estimated as similar to 1 ps, which is about 20 times lower than the value expected on the basis of the "energy gap law" for Delta E(S-2-S-1). To give a satisfactory interpretation of the properties of thiocoumarin in the relaxed vibrational configuration of the S-2 state, a very efficient electronic relaxation should have been considered for which a few possible mechanisms were discussed. A short lifetime of excited vibrational levels was not a consequence of electronic relaxation processes but was rather directly related to the rate of intramolecular vibrational redistribution.