Extraction of WO 42– and ReO 4– by Adogen-381, tricaprylmethylammonium chloride, Hyamine 10-X, trioctylphosphine oxide or dibenzylsulphoxide in xylene from HNO3, HCl or H2SO4 acid medium was investigated. Based on the separation factors obtained, the separation of ReO 4– from WO 42– was elucidated. ReO 4– was separated from WO 42– in high radiochemical purity: >99.9% by three successive extractions and strippings using Adogen-381 from HCl or HNO3 acid medium.