A　simple　halogen-bond-promoted　α-C−H　amination　of　ether/thioether　with　a　variety　of　N−H　compounds　has　been　accomplished.　In　the　presence　of　low-cost　and　readily　available　perfluorobutyl　iodide,　a　diverse　range　of　hemiaminal　ether　derivatives,　including　the　valuable　hydrazone　hemiaminal　ethers,　were　quickly　assembled　under　thermal　or　visible-light　irradiation　conditions.　Mechanistic　studies　suggest　that　a　halogen-bond　adduct　was　formed　and　a　radical　chain　pathway　might　be　operative.　Synthetic　application　of　the　method　has　been　demonstrated　via　the　preparation　of　the　anti-viral　and　anti-tumor　drug,　Tegafur.　(Figure　presented.).　©　2018　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim