The defect like the void or seam is frequently generated in the PCB (Printed Circuit Board) Via-Filling plating inside via hole. The organic additives including the accelerating agent, inhibitor, leveler, and etc. are needed for the copper Via-Filling plating without this defect for the plating bath. However, the decomposition of the organic additive reduces the lifetime of the plating bath during the plating process, or it becomes the factor reducing the reliability of the Via-Filling. In this paper, the interaction of each organic additives and the decomposition of additive were discussed. As to the accelerating agent, the bis (3-sulfopropyl) disulfide (SPS) and leveler the Janus Green B (JGB) and inhibitor used the polyethlylene glycol 8000 (PEG). The research on the interaction of the organic additives and decomposition implemented in the galvanostat method. The additive decomposition time was confirmed in the plating process from 0 Ah/l (AmpereHour/ liter) to 100 Ah/l with the potential change.