Photoreactions of 5-iododeoxyuridine (dIU) and dIU-containing oligonucleotides in aqueous solutions in the presence of various inorganic salts have been investigated. In the presence of NaCl and NaBr, dIU and dIU-containing oligonucleotides undergo an efficient photochemical halogen-exchange reaction to give dCIU and dBrU, respectively.