The complex [Cu2(1)2]2+ (1 = 1,3‐bis(1‐methyl‐1H‐benzimidazol‐2‐yl)benzene) undergoes slow oxidation by dioxygen in DMF solution to give the hydroxylated product [Cu2(2‐H)2]2+ (2 = 2,6‐bis(1‐methyl‐1H‐benzimidazol‐2‐yl)phenol) characterized by an X‐ray crystal‐structure analysis. The oxidation occurs much faster when CuII is mixed with 1 in the presence of H2O2, with 80% hydroxylation observed within a few minutes. The mononuclear complex formed with 1‐methyl‐2‐phenyl‐1H‐benzimidazole (3) shows no hydroxylation under these conditions. It is concluded that the hydroxylation requires the presence of a ligand capable of stabilizing a binuclear species, but no special coordinative activation of the copper is required.