A new unsymmetrical Schiff base ligand HL 1 , HBacabza, and its copper(II) complexes [Cu 2 L 1 2 (OAc) 2 ] (1) and [Cu 2 L 2 2 (N 3 ) 2 ]·2H 2 O (2) with HBacabza=3-(2-aminobenzylimino)-1-phenylbutan-1-one as HL 1 and its hydrolytically rearranged isomer 3-(2-aminomethylphenyleneimino)-1-phenylbutan-1-one as HL 2 , have been synthesized and characterized by elemental analyses and spectroscopic methods. The rearrangement of HL 1 to HL 2 occurs in a hydrolysis-recondensation process in the reaction of HL 1 with Cu(ClO 4 ) 2 ·6H 2 O and NaN 3 . The crystal structures of the ligand and its complexes have been determined by single crystal X-ray diffraction. The deprotonated Bacabza − coordinates to the metal center as a tridentate ligand. The acetate anion coordinates through one oxygen atom in complex 1 leading to a mono-atomic acetate oxygen-bridging dimeric copper(II) complex. Similarly, the azide anion coordinates through one nitrogen atom in complex 2 leading to a mono-atomic azide nitrogen-bridging dimeric copper(II) complex. The copper(II) ions adopt a distorted square pyramidal (4+1) coordination in these two complexes. The cyclic voltammetric studies of these complexes in N,N-dimethylformamide indicate that the reduction process corresponding to Cu II /Cu I is electrochemically irreversible in complex 1, presumably due to the structural changes during the course of redox reaction, and quasi-reversible in complex 2.