Donor–acceptor distance, orientation, and photoexcitation wavelength are key factors in governing the efficiency and mechanism of electron-transfer reactions both in natural and synthetic systems. Although distance and orientation effects have been successfully demonstrated in simple donor–acceptor dyads, revealing excitation-wavelength-dependent photochemical properties demands multimodular, photosynthetic-reaction-center model compounds. Here, we successfully demonstrate donor– acceptor excitation-wavelength-dependent, ultrafast charge separation and charge recombination in newly synthesized, novel tetrads featuring bisferrocene, BF2-chelated azadipyrromethene, and fullerene entities. The tetrads synthesized using multistep synthetic procedure revealed characteristic optical, redox, and photo reactivities of the individual components and featured “closely” and “distantly” positioned donor–acceptor systems. The near-IR-emitting BF2-chelated azadipyrromethene acted as a photosensitizing electron acceptor along with fullerene, while the ferrocene entities acted as electron donors. Both tetrads revealed excitation-wavelength-dependent, photoinduced, electron-transfer events as probed by femtosecond transient absorption spectroscopy. That is, formation of the Fc+–ADP–C60.− charge-separated state upon C60 excitation, and Fc+–ADP.−–C60 formation upon ADP excitation is demonstrated.