The TMSCF 3 -derived CuCF 2 CF 3 species has been successfully applied in pentafluoroethylation of organoboronates and terminal alkynes. By using 1,10-phenanthroline as a ligand, a broad range of (hetero)arylboronates and alkenylboronates were smoothly pentafluoroethylated under aerobic conditions. Furthermore, terminal alkynes can undergo aerobic cross-coupling with the TMSCF 3 -derived CuCF 2 CF 3 species in the absence of additional ligands.