Easy Access to the Copper(III) Anion [Cu(CF 3 ) 4 ] −

CuCl or pre‐generated CuCF 3 reacts with CF 3 SiMe 3 /KF in DMF in air to give [Cu(CF 3 ) 4 ] − quantitatively. [PPN] + , [Me 4 N] + , [Bu 4 N] + , [PhCH 2 NEt 3 ] + , and [Ph 4 P] + salts of [Cu(CF 3 ) 4 ] − were prepared and isolated spectroscopically and analytically pure in 82–99 % yield. X‐ray structures of the [PPN] + , [Me 4 N] + , [Bu 4 N] + , and [Ph 4 P] + salts were determined. A new synthetic strategy with [Cu(CF 3 ) 4 ] − was demonstrated, involving the removal of one CF 3 − from the Cu atom in the presence of an incoming ligand. A novel Cu III complex [(bpy)Cu(CF 3 ) 3 ] was thus prepared and fully characterized, including by single‐crystal X‐ray diffraction. The bpy complex is highly fluxional in solution, the barrier to degenerate isomerization being only 2.3 kcal mol −1 . An NPA study reveals a huge difference in the charge on the Cu atom in [Cu(CR 3 ) 4 ] − for R=F (+0.19) and R=H (+0.46), suggesting a higher electron density on Cu in the fluorinated complex.