The　development　of　new　strategies　for　synthesis　of　trifluoromethylthiolate　compounds　is　of　considerable　importance　in　pharmaceuticals,　agrochemicals,　and　advanced　materials.　Accordingly,　currently　much　attention　is　being　devoted　to　the　development　of　effective　methods　and　reagents　for　their　synthesis.　In　contrast,　considerably　less　effort　has　been　afforded　to　the　development　of　preparing　C-SeCF3　bonds.　Herein　we　report　a　concise　route　to　synthesize　a　family　of　copper(I)　trifluoromethylselenolate　reagents　by　the　reaction　of　CuI　with　the　Ruppert＇s　reagent　(Me3SiCF3),　KF,　and　elemental　selenium　in　the　presence　of　dinitrogen　ligands　in　CH　3CN　at　room　temperature.　The　reagent　[Cu(bpy)(SeCF3)]　2　was　proven　to　be　air-stable　and　highly　efficient　for　nucleophilic　trifluoromethylthselenolation　of　a　broad　range　of　(hetero)aryl　halides　and　alkyl　halides.　This　method　represents　a　powerful　protocol　for　the　construction　trifluoromethylselenolate　compounds.　Copyright　©　2014　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.