The extraction behavior of uranium(VI) from thiocyanate medium with dibenzo-18-crown-6 (DBC) in nitrobenzene and the effects of alkali cations on the extraction were investigated. The results showed that the uranium (VI) can be effectively extracted in the presence of potassium cation, uranium (VI) is extracted as complex anionic species UO2(SCN)-3, and the stoichiometry of the extracted complex is KUO2(SCN)32DBC(o).