Photoexcitation of a zinc phthalocyanine-perylenediimide (ZnPc-PDI) dyad and a bis(zinc phthalocyanine)-perylenediimide [(ZnPc) 2-PDI] triad results in formation of the triplet excited state of the PDI moiety without the fluorescence emission, whereas addition of Mg (2+) ions to the dyad and triad results in formation of long-lived charge-separated (CS) states (ZnPc (*+)-PDI (*-)/Mg (2+) and (ZnPc) 2 (*+)-PDI (*-)/Mg (2+)) in which PDI (*-) forms a complex with Mg (2+). Formation of the CS states in the presence of Mg (2+) was confirmed by appearance of the absorption bands due to ZnPc (*+) and PDI (*-)/Mg (2+) complex in the time-resolved transient absorption spectra of the dyad and triad. The one-electron reduction potential ( E red) of the PDI moiety in the presence of a metal ion is shifted to a positive direction due to the binding of Mg (2+) to PDI (*-), whereas the one-electron oxidation potential of the ZnPc moiety remains the same. The binding of Mg (2+) to PDI (*-) was confirmed by the ESR spectrum, which is different from that of PDI (*-) without Mg (2+). The energy of the CS state (ZnPc (*+)-PDI (*-)/Mg (2+)) is determined to be 0.79 eV, which becomes lower that of the triplet excited state (ZnPc- (3)PDI*: 1.07 eV). This is the reason why the long-lived CS states were attained in the presence of Mg (2+) instead of the triplet excited state of the PDI moiety.