The photophysical properties of the oligosilane-bridged zinc porphyrin-fullerene dyads have been investigated. Dependence of the rate of the relaxation processes of the singletexcited state of the ZnP moiety of the dyads on the oligosilane linker was mostly ascribable to the conformational differences of the silicon chain. The charge-separated state with sub-microsecond lifetime was observed in the time-resolved absorption measurements of benzonitrile solution of the dyads. The lifetime of the radical-ion pair scarcely depended on the length and little on the conformation of the oligosilane linkage, which suggests that the super-exchange mechanism disciplines the charge recombination process. Copyright The Electrochemical Society.