The electron spin dynamics associated with intramolecular electron transfer in a photosynthetic model system, which consists of a linear structure of the type A-B-C, is described. In this structure, donor A is a p-methoxyaniline, chromophore B is a 4-amino-1,8-naphthalimide, and acceptor C is a 1,4:5,8-napththalenediimide. This supramolecular electron donor-acceptor array was isotropically oriented in toluene, and anisotropically oriented in liquid crystal matrices, and studied by time-resolved electron paramagnetic resonance spectroscopy. Photoexcitation of B results in a two-step electron transfer to yield the radical ion pair, A(.+)-B-C-.-. Charge recombination within A(.+)-B-C-.- produces a molecular triplet state, A-B-C-3*, which exhibits the unique spin-polarized electron paramagnetic resonance signal that has been observed only in photosynthetic reaction-center proteins.