Six Schiff base copper() complexes have been prepared and characterized, elemental analyses, mass, IR and electronic spectra, µ eff and X-ray crystal structures being obtained. The X-ray study shows that the geometry around the metal atom is square planar for one of the complexes only and distorted square planar for the others. Electrochemical studies on the complexes, though revealing a dependence of the Cu()/Cu() potentials on electronic effects, also show that these are independent of the structure observed in the solid state. Besides, EPR studies of these complexes in DMF solution at 193 K suggest that the geometry of these complexes in solution is different to that observed in the solid state by X-ray crystallography.