A dithienylethene (DTE)-porphyrin (P)-fullerene (C(60)) triad molecule in which intramolecular photoinduced electron transfer is controlled by the photochromic DTE moiety has been prepared. Irradiation of the molecule with visible light gives the open form of the dithienylethene (DTEo). Excitation of the porphyrin gives DTEo-(1)P-C(60), which undergoes photoinduced electron transfer with a time constant of 25 ps to generate DTEo-P(.+)-C(60)(.-). Irradiation with ultraviolet light produces the closed form of the dithienylethene (DTEc). Excitation of DTEc-P-C(60) yields DTEc-(1)P-C(60), whose porphyrin first excited singlet state is quenched in 2.3 ps by singlet-singlet energy transfer to DTEc, generating (1)DTEc-P-C(60) and precluding significant photoinduced electron transfer. Such highly reversible photonically controlled intramolecular photoinduced electron transfer may eventually be useful in the design of photonic or optoelectronic devices.