A desulfurization process for dibenzothiophene (DBT) and its derivatives such as 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) by combination of photochemical reaction and liquid-liquid extraction has been investigated. In this, the DBTs dissolved in tetradecane were quantitatively photodecomposed by the use of a high-pressure mercury lamp and were removed to the water phase as SO42- at conditions of room temperature and atmospheric pressure. The order of reactivity for the DBTs was DBT < 4-MDBT < 4,6-DMDBT, thus indicating a different tendency from that reported for the hydrodesulfurization method. The desulfurization yield of commercial light oil, however, by the proposed method was only 22% following 30 h irradiation and was caused mainly by the depression of the photoreaction of DBT by the presence of aromatic compounds in the light oil.