Compounds containing the tetrazole scaffold have drawn an intense interest in recent years due to their widespread applications in medicine, food industry, photography, agriculture and in automobile industry. As a result, the structure and reactivity of tetrazolic compounds has been extensively studied. However, the related tetrazolethiones have not received much attention. Our research group is interested in studying the chemistry and biological significance of the tetrazolethiones. Here in, we will present the photochemical properties and reactivities of 1,4-disubstituted tetrazolethiones 1a – d. We will present the synthesis of tetrazolethiones 1a – d and discuss the kinetics of their conversion upon irradiation to the corresponding carbodiimides 2a – d and ureas 3a – d. The solvent effects on the photochemistry of 1a – d will also be discussed. Quantum yields for the photodecomposition of 1a – d have been determined by using the ferrioxalate actinometer and will be presented.