We experienced a case with Graves' disease in which radioiodine treatment failed probably because of intentional spitting out of capsules of radioactive iodide. Chemical analysis of the substances collected from the trash in the treatment room demonstrated that its profile was the same as that of the capsules for radioiodine administration. Measurement of the iodine concentrations in a blood sample obtained at 24 h after the administration of radioiodine indicated that the patient showed iodine excess. These findings suggest that this may be a case of Munchausen syndrome.