A new type of TeFe3(CO)9-incorporated dicopper NHC complex was obtained directly from one-pot reactions. By the introduction of the cluster anion [TeFe3(CO)9](2-) and NHCs as the ligands, these di-Cu(i)-based complexes exhibited pronounced catalytic activities toward the homocoupling of arylboronic acids with low Cu loadings and high yields (up to 98%).