Chloride ions and their interactions with two organic smoothing additives - Cyquest® N-900 and HydroStar® 4208 - during copper electrodeposition were explored using cyclic voltammetry and electrochemical impedance spectroscopy. The results revealed that chloride ions, up to a concentration of 40 mg/L, depolarized the copper deposition reaction. A combination of chloride ions and Cyquest N-900 inhibited the depolarization reaction during copper electrodeposition. It is proposed that the chloride ions acted as bridging ligands between copper and Cyquest N-900. Addition of HydroStar at a concentration of 2.5 mg/L depolarized the copper deposition reaction when no chloride ions were present. This behavior did not change with the addition of chloride ions at the concentrations tested, indicating that chloride ions and the polysaccharide do not interact.