Fluorescence emission from the first, S1, and second, S2, excited π-electronic singlet states to the singlet ground state, S0, has been observed for a number of aromatic molecules in dilute, deoxygenated n-heptane solutions. Detailed fluorescence spectra from S1 and S2 for 3,4-benzpyrene and 1,12-benzperylene over the temperature range –90 to + 90°C are reported. The S2 fluorescence is very strongly dependent on temperature and it results mostly from thermal repopulation of S2 from S1. The ratio, R, of the integrated fluorescence quantum intensity from S2 to that from S1 is 0.09 at –90°C and 0.8 at +90°C for 1,12-benzperylene. For 3,4-benzpyrene, R= 0.06 at –90°C and R= 0.4 at +90°C. These studies show that fluorescence emission from the second excited π-singlet state of aromatic molecules in solution is not uncommon and that the internal conversion process cannot be regarded as being completely irreversible in these systems.