Supramolecular triads of the type (donor-1)−acceptor:(donor-2) composed of free-base porphyrin, fullerene, and zinc porphyrin, have been formed by a “covalent-coordinate” approach. Toward this, two diads, namely, 5-(3‘-(2‘ ‘-(3‘ ‘‘ or 4‘ ‘‘-pyridyl)fulleropyrrolidinyl-N)ethoxyphenyl)-10,15,20-triphenylporphyrin, bearing C60 as acceptor and free-base porphyrin, H2P, as donor were first synthesized. The diads and self-assembled supramolecular triads, which were formed by coordinating the pyridine group located on the diads to zinc tetraphenylporphyrin, ZnP, have been characterized by semiempirical PM3, electrochemistry, and steady-state and time-revolved spectroscopic techniques. Subpicosecond and nanosecond transient absorption spectral studies of diads revealed the occurrence of the electron transfer from the H2P moiety to the C60 entity via the excited singlet state of H2P. Clear evidence for the formation of triads in o-dichlorobenzene was obtained from the steady-state and time-resolved fluorescence me...