Free base and zinc porphyrins are linked with fullerene (C-60) through beta,beta`-pyrrolic positions rather than meso-positions by Diels-Alder reaction of monoanthraporphyrins (H2P-mA and ZnP-mA) and C-60 to afford a pi-expanded free base porphyrin-fullerene dyad (H2P-C-60) and its zinc porphyrin-fullerene dyad (ZnP-C-60) in 86 and 51% yield, respectively The X-ray crystallographic analysis of ZnP-C-60 showed two comma-shaped swirls-like structure in a unit cell The intramolecular center-to-center and edge-to-edge distances between the porphyrin and fullerene moieties were 11 5 and 2 5 angstrom, respectively The porphyrins and fullerenes were packed in layer-by-layer structure and the porphyrins lied down in parallel The Intermolecular center-to-center distances between the neighboring fullerenes were 10 252, 10028, and 10 129 angstrom, which were less than typical van der Waals distance and the pi-pi interaction spread two-dimensionally The energy of the charge-separated (CS) state of ZnP-C-60 (1 11 eV) determined by differential-pulse voltammetry measurements in benzonitrile is significantly lower than those of zinc porphyrin-C-60 dyads linked at meso positions because of the low oxidation potential of the a-expanded ZnP moiety The CS energy of ZnP-C-60 in a nonpolar solvent such as toluene (1 40 V) is lower than the triplet excited state of C-60 (C-3(60)*), enabling us to attain a longed lived triplet CS state (8 1 mu s) in toluene, detected by nanosecond laser flash photolysis experiments The distance between unpaired electrons in the triplet CS state was determined by the EPR spectrum to be 9 1 angstrom, which agreed with the distance between a zinc atom of the porphyrin and a carbon edge of C-60 in the crystal structure of ZnP-C-60 The rate constants of photoinduced electron transfer and back electron transfer of H2P-C-60 and ZnP-C-60, which were determined by femtosecond and nanosecond laser flash photolysis measurements, were analyzed in light of the Marcus theory of electron transfer