Thiosemicarbazones and their corresponding complexes represent a very interesting category of compounds which possess a wide spectrum of applications in bioinorganic chemistry and medicine [1, 2]. Due to their coordination capacity thiosemicarbazones are excellent reagents for the design of transition metal complexes [3]. As a continuation of our previous researches in the field of complexes with azomethine ligands derived from pyridoxal we prepared new ligands from the thiosemicarbazones category. The structures of ligands were characterized by elemental analysis, IR and 1H and 13C NMR spectroscopy.figureUsing the new thiosemicarbazone type ligands we designed several copper(II) complexes. In order to evaluate the influence of the anions on the geometry of the complexes a series of inorganic copper(II) salts were used. The complexes were studied based on multiple physico-chemical techniques like IR and electronic spectroscopy, magnetic studies, thermal studies and single crystal X-ray diffraction. A direct relation between the nature of the contraions from the metal salts and the stereochemistry of the complexes can be observed.