The fluorescence intensity of khellin-dimethylfumarate C$_4$-cycloadduct (KDF) is very sensitive to temperature and to the nature of solvents, especially hydrogen-bonding ability. The fluorescence quantum yields of KDF in ethanol and isopentane at 77K are 0.73 and 0.54, respectively, both of which are much larger than the room temperature values. The phosphorescence lifetime is very long and decreases with decreasing the solvent polarity. The phosphorescence and fluorescence quantum yield ratio is very small and decreases with decreasing solvent polarity. The solvent relaxation plays an important role in the excited states of KDF. The internal conversion is a major decay process of the excited singlet state of KDF in all the solvents used at room temperature.