This　article　describes　the　new　economic　decarboxylative　trifluoromethylating　reagent　[Cu(phen)(O2CCF3)]　(1;　phen=1,10-phenanthroline)　and　the　efficient　difluorocarbene　precursor　[Cu(phen)2][O2CCF2Cl]　(2).　Treatment　of　copper　tert-butoxide　with　phen　and　subsequent　addition　of　trifluoroacetic　acid　or　chlorodifluoroacetic　acid　afforded　air-stable　complexes　1　and　2,　respectively,　which　were　characterized　by　X-ray　crystallography.　The　copper(I)　ion　in　1　is　coordinated　by　a　bidentate　phen　ligand,　a　monodentate　trifluoroacetate　group,　and　a　molecule　of　CH3CN　in　a　distorted　tetrahedral　coordination　geometry.　The　molecular　structure　of　2　adopts　an　ionic　form　that　consists　of　a　[Cu(phen)2]+　cation　and　a　chlorodifluoroacetate　anion.　Complex　1　reacted　with　a　variety　of　aryl　and　heteroaryl　halides　to　form　trifluoromethyl　(hetero)arenes　in　good　yields.　The　corresponding　Hammett　plot　exhibited　a　linear　relationship　and　a　reaction　parameter　(ρ)=+0.56±0.02,　which　indicated　that　the　trifluoromethylation　reaction　proceeded　via　a　nucleophilic　reactive　species.　Complex　2　reacts　with　phenols　to　produce　aryl　difluoromethyl　ethers　in　modest-to-excellent　yields.　Mechanistic　investigations　revealed　that　the　difluoromethylation　reaction　proceeds　by　initial　copper-mediated　formation　of　difluorocarbene　and　subsequent　concerted　addition　of　difluorocarbene　to　the　phenol　to　form　a　three-center　transition　state.　©　2016　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.