A series of [Cu(NN')]2(OTf)2 complexes containing pyridine-triazole ligands [OTf = OSO2CF3; NN' = NN'Ph (1), NN'hex (2), NN'py (3)] with different substituents at the triazole N4 position or 2,2'-bipyridine (bpy; 4) have been synthesized. Crystal structures of 1 and 3 reveal a trans-isomer with strong preference for regular-type triazole coordination (for 3) whereas the Cu-bipyridine complex 4 is more stable in a cis-form. Cyclic voltammetry of 1-4 suggest that the electron-donating strength follows the trend: bpy > NN'py > NN'hex ~ NN'Ph. The catalyst systems consisting of 5 mol% CuOTf2/NN'/TEMPO (TEMPO = (2,2,6,6-tetramethylpiperidin-1-yl)oxy) in the presence of 2x2.0 cm 2 Cu 0 sheets as a reducing agent and 10 mol% N-methylimidazole (NMI) exhibit good activities for aerobic oxidation of benzyl alcohol to benzaldehyde. Catalytic studies have shown that the activities were higher with more electron-rich N-based ligands. Furthermore, oxidation of aliphatic alcohols such as 1-hexanol and 2-methyl-1-pentanol using the Cu catalyst system with the NN'py ligand at room temperature afforded the corresponding aldehydes in >99% and 46% yields, respectively after 24 h.