The purpose of this work is to study the electrocrystallization behavior of the copper deposit on pure titanium substrate. The electroplating was conducted at 0.7 A/cm(2), 65 degrees C in cupric sulfate-sulfuric acid bath with various chloride additions (45-350 ppm). Initial growth morphology and microstructure of the deposit were examined with a field-emission scanning electron microscope (FESEM) and a high-resolution transmission electron microscope integrated with an energy-dispersive X-ray spectrometer. Results of cathodic polarization and galvanostatic plating experiments show that the increasing concentration of chloride ions in the plating bath would significantly increase the cathodic potential. This cathodic potential increase was found to be induced by the presence of CuCl precipitates on the cathodic surface as well as on the copper cluster formed during the electrocrystallization process. At the initial plating stage, both copper and hexagonal-shaped CuCl precipitates were produced simultaneously. Eventually, the pyramid-shaped CuCl precipitates were observed, which consisted of many parallel hexagonal planes stemming from a screw dislocation. The polarization effect of CuCl precipitate on the Ti substrate was further confirmed and clarified. Through measurement of the electrode response and investigation of the deposit using FESEM, it was observed that under identical electroplating conditions, much less CuCl forms on a copper substrate in the initial stages than on a titanium substrate, leading to lower polarization. (c) 2005 The Electrochemical Society.