The Schiff base ligands, 2-hydroxy-N-cyclohexyl-1-naphthaldimine (I), and 3-hydroxy-N-cyclohexyl-2-naphthaldimine (II), and their corresponding Cu I I complexes (1-2) respectively were synthesized and characterized. The crystal and molecular structures of bis-{(cyclohexyl)[2-oxo-1H-naphth-1-ylidene)-methyl]aminato}copper(II) (1) and bis-{(cyclohexyl)[(3-oxo-2H-naphth-2-ylidene)-methyl]aminato} copper(II) (2), were determined. The X-ray diffraction study shows that the geometry around the metal atom for (1), is stepped square planar with a step of 1.063 9 while for (2), the geometry around the metal atom is distorted square planar with an angle between the coordination planes O(1)-Cu-N(1) and O(1a)-Cu-N(1a) of 39.9°. Electrochemical studies show a dependence of the Cu I I Cu I potentials on the ligand structure.