Highly preferred orientation copper coatings show excellent functions. Many factors affect copper coatings’ crystal preferred orientation, and additives are one of the factors. Copper coatings were prepared at 0.040 A/cm 2 and 0.150 A/cm 2 by constant current, respectively. The electrolytes were acid CuSO4 solution with additives MPS (3-mercapto propane sodium sulfonate) or SPS(poly-2-sulfur-2-propane sodium sulfonate), and their combinations with PEG (polyethylene glycol) and Cl -. X-ray diffraction shows that (220) lattice plane fully preferred orientation is obtained at the higher current density 0.150 A/cm 2 with the combination of MPS+Cl - or SPS+Cl -. But different preferred orientations are obtained with only MPS or SPS, or other combinations, such as MPS+PEG, MPS+PEG+Cl -, SPS+PEG, SPS+PEG+Cl -. Using different combinations of additives is an effective method to obtain highly preferred orientation lattice planes earlier in the process of electrodeposition.