The synthesis, isolation, and full characterization of a series of NHC-copper perfluoro-alkoxide complexes are reported. Their exceptional stability resides with the steric hindrance of the nonafluoro-tert-butyl alkoxide moiety, which exhibits a strong electron withdrawing effect. These new Cu(I) complexes are synthons that can permit the activation of acidic N-H and S-H bonds. The well-defined [Cu(IPr)(OC(CF3)3)] was investigated as a pre-catalyst in the Chan-Evans-Lam reaction.