Abstract: This paper studies the effects of coarsening layer surface based on the basic components of plating solution, additive content, current density and temperature by simulating the technology of electrolytic copper foil production to find a new complex additives and routes replacing the arsenic additives in the existing coarsening technology of copper foil. The best formula and condition of arsenic-free coarsening technology is researched by comparing the coarsening effect from metallurgical microscope. The experimental results show that the new complex additives of stannous sulfate and sodium tungstate can replace the arsenic additives in the existing technology by achieving superior environmental performance.