In Taiwan, the turbidity of raw water for fresh water treatments can sometimes reach as high as 40 000 NTU due to intensive rainfall, especially in typhoon seasons. In response, water works often apply large quantities of coagulants such as polyaluminium chloride (PACl). In this study, simulated and natural highly turbid water was coagulated with two PACls, a commercial product (PACl-1) and a laboratory product (PACl-E). The Al species distributions of PACl-1 and PACl-E under various pH conditions were determined, and the corresponding coagulation efficiency was evaluated. The PACl-E has a wider range of operational pH, while the efficiency of PACl-1 peaks at around neutral pH. For simulated water up to 5000 NTU, the PACl-E was superior to PACl-1 at low dosage and in the pH range studied. Similar results were discovered with natural water, except that when the turbidity was extremely high, the coagulation efficiency of PACl-E decreased significantly due to the presence of large amounts of organic matter. The coagulation of PACl-E was closely related to the content of polycationic aluminium (Al13) while that of PACl-1 was dictated by the amount of Alc. The sludge from PACl-E coagulation had better dewaterability when the optimum dosage was applied. The experimental results suggest that for natural water up to 5000 NTU, PACl containing high Al13 species is recommended for coagulation. In cases when the water contains high organic matter, efficient coagulation depends upon enmeshment by amorphous aluminium hydroxide.