The fluorescence quantum yield of khellin is sensitive to temperature and to the nature of solvents, especially the proton-donating ability in solute-to-solvent hydrogen bonding. The intersystem crossing quantum yields are 0.4 and 0.15 in acetonitrile and ethanol, respectively. The fluorescence quantum yields in ethanol and isopentane at 77 K are 0.61 and 0.07, respectively, both of which are much larger than the values at room temperature. The phosphorescence lifetime is relatively long and decreases with decreasing solvent polarity. The phosphorescence to fluorescence quantum yield ratio is very small and remains unchanged in various solvents. The results suggest that internal conversion is an important decay channel of the excited singlet state of khellin, especially in the hydrogen-bonding hydroxyl solvents.