Photoinduced electron-transfer processes of a newly synthesized rodlike covalently linked ferrocene-naphthalenediimide-[60]fullerene (Fc-NDI-C(60)) triad in which Fc is an electron donor and NDI and C(60) are electron acceptors with similar first one-electron reduction potentials have been studied in benzonitrile. In the examined Fc-NDI-C(60) triad, NDI with high molar absorptivity is considered to be the chromophore unit for photoexcitation. Although the free-energy calculations verify that photoinduced charge-separation processes via singlet- and triplet-excited states of NDI are feasible, transient absorption spectra observed upon femtosecond laser excitation of NDI at 390 nm revealed fast and efficient electron transfer from Fc to the singlet-excited state of NDI ((1)NDI*) to produce Fc(+)-NDI(*-)-C(60). Interestingly, this initial charge-separated state is followed by a stepwise electron transfer yielding Fc(+)-NDI-C(60)(center dot-). As a result of this sequential electron-transfer process, the lifetime of the charge-separated state (tau(CS)) is elongated to 935 ps, while Fe(+)-NDI(center dot-) has a lifetime of only 11 ps.