Charge transfer through DNA oligonucleotides has been investigated for potential applications of DNA into molecular electrooptic switching devices. Electrons were injected using gold electrode probes where DNA oligomers were adsorbed that are separated in medium. The results show that increased adsorption of DNA reduces the ionization current due to the combined effect of charge transfer through DNA and surface-limited charge transport. The probe-based charge injection was extended to examine the capability of extinguishing fluorescence of Cy3 dye molecules attached to DNA. It is expected that the results may be employed to implementing a novel electrooptic switching device based on DNA molecules.