A fluorescent photochromic molecule, which is composed of a photochromic diarylethene (DE) and a fluorescent perylenebisimide (PBI), was synthesized and its fluorescence photoswitching was studied. The fluorescence quantum yield of the open-ring isomer is constant irrespective of solvent polarity, while that of the closed-ring isomer decreases with an increase in the dielectric constant of solvents. Femtosecond time-resolved transient and fluorescence lifetime measurements revealed that the fluorescence quenching of the closed-ring isomer is attributed to the intramolecular electron transfer from the PBI chromophore to the DE unit.