Coagulation behavior of Al13 species was examined in synthetic water with high alkalinity and high humic acid concentration from viewpoint of the transformation of Al hydrolysis products during the coagulation process. The results indicated that coagulation efficiency of Al coagulants positively correlated with the content of Al13 in the coagulation process. Aluminum chloride (AlCl3) was more effective than polyaluminum chloride (PACI) in removing turbidity and dissolved organic matter in the synthetic water because AlCl3 could not only generate Al13 species but also function as pH control agent in the coagulation process. During coagulation process pH control can improve coagulation process through regulating Al speciation, and AlCl3 benefited most from pH control.