The reaction of copper(II) salts with Bpy-TEMPO and Tpy-TEMPO (Bpy-TEMPO = [2,2′]Bipyridinyl-5,5′-dicarboxylic acid bis-[(2,2,6,6-tetramethyl-1-oxy-piperidin-4-yl)-amide]; Tpy-TEMPO = 2,2,6,6-tetramethyl-4-(2,2′:6′,2″-terpyridin-4′-yloxy)piperidin-1-oxyl) gave dinuclear Bpy-TEMPO-Cu2(1) and mononuclear Tpy-TEMPO-Cu (2), respectively. The Cu(II) complexes were characterized by single crystal X-ray analysis. In1, Cu(II) has a distorted square pyramidal coordination geometry, with a bridging chloride as the axial ligand. The Cu(II) core in2also exhibited a distorted square pyramidal coordination geometry, with one chloride as an axial ligand. Weak interactions such asπ-interactions and hydrogen bonds are observed in both complexes. When applied as catalysts for the oxidation of benzyl alcohol to benzaldehyde in air,1exhibited higher activity than2for reactions in o-xylene at 60°C with DBU as a base. High yield (67%) of benzaldehyde was observed when using1as a catalyst in a solution of o-xylene with DBU at 60°C. [ABSTRACT FROM AUTHOR]