The effects of plating process on the surface coverage of the accelerator were investigated in terms of Cu superfilling for device metallization. When a substrate having 500 nm-wide trench patterns on it was immersed in an electrolyte containing poly (ethylene glycol) (PEG)-chloride ion ($Cl^-$)-bis(3-sulfopropyl) disulfide (SPS) additives without applying deposition potential for such a time of about 100s, voids were generated inside of the electrodeposit. In time-evolved electrochemical analyses, it was observed that the process (immersion without applying potential) in the electrolyte led to the build-up of high initial coverage of SPS-Cl on the surface, resulting in the fast saturation of the coverage. Repeated experiments suggested that the fast saturation of SPS-Cl failed in superfilling while a gradual increase in the SPS-Cl coverage through competition with initially adsorbed PEG-Cl enabled it. Consequently, superfilling was achievable only in the case of applying the plating potential as soon as the substrate is dipped in an electrolyte to prevent rapid accumulation of SPS-Cl on the surface.