The crystal structure, surface morphology and preferred orientation of the copper electrodeposit were investigated by the using sulfate bath with SiO 2 suspensions and the cathode substrate Au sputtered. As by the addition of colloidal silica in copper electrolytic bath and Au pre-coating on substrate, the crystal particles of deposits was fined-down, made uniform and the account of particles were increased. Hardness of copper electrodeposits with colloidal silica increased about 15% in comparison with that of pure copper deposit film and (111), (200) and (311) plane of X-ray diffraction patterns were almost swept away, so preferred orientation of the copper deposits changed from (111) to (110) plane by codeposit SiO 2 and precoating the substrate.