The electrochemical behavior of additives is severely affected by convection, which determines the filling process of through ceramic holes (TCHs). VMS contained a high concentration of cupric and a low concentration of H 2 SO 4 was prone to achieve a good leveling effect. The additives including thiazolinyl polydipropyl sulfonate (SH110) as the accelerator, polyethylene glycol (PEG) as the suppressor, and nitrotetrazolium blue chloride (NBT) as the leveler, respectively. The electrochemical measurements such as galvanostatic and cyclic voltammetric measurements were employed to evaluate the electrochemical behaviors of additives. The additive mixture PEG+SH110+NBT significantly promotes copper deposition under weak convection and inhibits copper deposition under strong convection, which is suitable for the defect-free filling of TCHs with an aspect ratio larger than 4.75, and the copper film on the ceramic substrate is smooth and bright.