Ferrocyanide and ferricyanide ions have strong coagulation ability in a natural water system due to their high valences. Studies with aluminum oxide turbid waters showed significant differences in coagulation between simple ions (Cl-, SO4/2-, Fe(CN)6/3-, Fe(CN)6/4-) and other species (H2PO4/-) that interact chemically with the oxide surface. The evidence suggested that the adsorption of ferrocyanide and ferricyanide on aluminum oxide surface is an outer-sphere reaction. The linear relationship between the logarithm of the significant coagulation concentration and Schultz-Hardy ratios indicated that the coagulation obeyed the DLVO rule. Therefore, it is concluded that the coagulation of aluminum oxide by ferrocyanide and ferricyanide is essentially caused by compression of the electric double layer rather than by charge neutralization.