The effects of additives on the Zn electrodeposition in chloride-based electrolyte were investigated using circulation cell with three electrodes system. The cathodic polarization increased with the addition of polyethylenglycol (hereafter PEG) in electrolyte. This was attributed to the adsorption of the additives on the electrode and the inhibition of migration of metal ion. The PEG, however, did not have any noticeable effect on the properties of plating solutions at the concentration used. The effect of PEG on the electrocrystallization was related to its molecular weight. With the increase of molecular weight, the cathodic polarization increased, while the surface roughness was improved with the decrease of brightness. Especially, the PEG mixed with different molecular weights was the most effective. The orientation and the type of the deposited grains were changed and refined by PEG, which resulted in the modification of deposited surface roughness and brightness.