Increasing cycle of water circulation in industrial cooling water system caused accumulation of dissolving materials in circulating water. Subsequently, the problems including scaling, fouling, corrosion and slime occurred. The multiple oxidants including chlorine dioxide, ozone, peroxide hydrogen, and chlorine were prepared using diaphragm electrolysis method to alleviate the problems above in the cooling system. Meanwhile multiple oxidants can also inhibit the accumulation of biological dirt and erosion effectively. The efficiency of multiple oxidants to inhibit precipitation of magnesium carbonate and calcium carbonate can be increased by adjustment of pH value in the whole pipeline system to reduce corrosion rate of the pipeline and to achieve energy-water saving goal. The results showed that the high efficiency of chlorine dioxide mixture was an excellent bio-corrosion inhibitor and bio-accumulation bactericide. The residue concentration of mixture oxidants are at the range of 0.05 ~ 0.25 mg ClO2/L that is high enough to restrain the growth of micro-organisms.