The N4O3 coordinating heptadentate ligand afforded binuclear complex [Cu-2(H2L)(mu-OH)](ClO4)(2) (1) and [Cu-2(L)(H2O)(2)]PF6 (2). In complex 1, two copper ions are held together by mu-phenoxo and mu-hydroxo bridges, whereas in complex 2, the copper centers are connected only by a mu-phenoxo bridge. In 1, both the Cu(II) centers have square pyramidal geometry (tau = 0.01-0.205), whereas in the case of 2, one Cu(II) center has square pyramidal (tau = 0.2517) and other one has square based pyramidal distorted trigonal bipyramidal (tau = 0.54) geometry. Complexes 1 and 2 show an strong intramolecular and very weak antiferromagnetic interaction, respectively. Density-functional theory calculations were performed to establish the magneto structural correlation between the two paramagnetic copper(II) centers, Both of the complexes display a couple of one-electron reductive responses near -0.80 and -1.10 V. The complexes show significant catalytic activity at pH 8.5 on the oxidation of 3,5-ditert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylqui none (3,5-DTBQ), and the activity measured in terms of k(cat) = 29-37 h(-1).