The distance dependence of photoinduced electron transfer in duplex DNA was determined for a family of synthetic DNA hairpins in which a stilbene dicarboxamide forms a bridge connecting two oligonucleotide arms. Investigation of the fluorescence and transient absorption spectra of these hairpins established that no photoinduced electron transfer occurs for a hairpin that has six deoxyadenosine-deoxythymidine base pairs. However, the introduction of a single deoxyguanosine-deoxycytidine base pair resulted in distance-dependent fluorescence quenching and the formation of the stilbene anion radical. Kinetic analysis suggests that duplex DNA is somewhat more effective than proteins as a medium for electron transfer but that it does not function as a molecular wire.