Chemical mechanical polishing (CMP) of copper in ammonium hydroxide based slurry in the presence of hydrogen peroxide was investigated. The polishing trend was found to be similar to that exhibited by other slurries containing hydrogen peroxide and various complexing agents used for Cu CMP. When the hydrogen peroxide concentration is increased, the polish rate increases, reaches a maximum and then decreases. The location and the magnitude of the maximum depend on the ammonium hydroxide concentration. The dissolution of copper in the NH4OH-hydrogen peroxide solution was probed by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) experiments. Electrical equivalent circuit (EEC) and reaction mechanism analysis (RMA) were employed to determine the mechanistic reaction pathway of Cu dissolution in NH4OH-hydrogen peroxide system. Based on the RMA analysis, a four step catalytic mechanism with two adsorbed intermediate species is proposed.