Two copper(II) complexes, [Cu2L2(μ1,1-N3)2]·2CH2Cl2 (1) and [CuL(μ1,5-dca)]n (dca = dicyanamide) (2) have been synthesized using a tridentate Schiff base ligand, 1-[(3-methylamino-propylimino)-methyl]-naphthalen-2-ol (HL) and azide or dicyanamide as co-ligand. Both complexes are characterized by elemental analysis, IR and UV-Vis spectroscopy and single crystal X-ray diffraction studies. The coordination geometry around the copper center in complex 1 is as an elongated (4 + 1) square pyramid and that in complex 2 is square planar with the tridentate Schiff base ligand in the basal plane. Complex 1 is a centrosymmetric dimer in which metal centers are connected by the double μ-1,1-azido bridges. On the other hand, complex 2 is a 1D zigzag chain in which metal centers are connected by μ1,5-N(CN)2 ligands. The catecholase like activity for both complexes have been studied by using 3,5-di-tert-butylcatechol (3,5-DTBC) as the substrate. Complex 1 shows higher activity (kcat = 40.8 h-1) than that of complex 2 (27.6 h-1) towards such oxidation reaction. © 2015 Elsevier B.V. All rights reserved.