The [Cu2(μ‐O)2]2+ and [Cu2(μ‐η2:η2‐O)2]2+ motifs with coordinated N,N,N‐tribenzyl‐1,4,7‐triazacyclononane and N,N,N‐triisopropyl‐1,4,7‐triazacyclononane auxiliary ligands in their reaction with flavonol do not lead to ring scission products of the heterocycle, but the formation of the corresponding (flavonolato)copper(II) complexes [Cu(fla)(Bz‐TAC)]ClO4 and [Cu(fla)(iPr‐TAC)]ClO4. The subsequent oxygenolysis of the coordinated flavonolate ligand leads to O‐benzoylsalicylate at elevated temperature, resulting in the enzyme mimicking products [Cu(O‐bs)(Bz‐TAC)]ClO4, [Cu(O‐bs)(iPr‐TAC)]ClO4) as well as carbon monoxide. The X‐ray structures of [Cu(fla)(Bz‐TAC)]ClO4, [Cu(O‐bs)(Bz‐TAC)]ClO4, and [Cu(O‐bs)(iPr‐TAC)]ClO4) are presented. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)