Four new well-defined CuI complexes bearing a C2F5 ligand have been prepared and fully characterized: [(Ph3P)2CuC2F5] (2), [(bpy)CuC2F5] (3), [(Ph3P)Cu(phen)C2F5] (4), and [(IPr*)CuC2F5] (5). X-ray structures of all four have been determined, showing that the C2F5-ligated Cu atom can be di- (5), tri- (2 and 3), and tetracoordinate (4). The mixed phen-PPh3complex 4 is a highly efficient fluoroalkylating agent for a broad variety of acid chlorides. This high-yielding transformation represents the first general method for the synthesis of RCOC2F5from the corresponding RCOCl.