Poly(aluminum chloride)(PAC) solutions of different basicity were prepared from pure aluminum foil and hydrochloric acid. Aluminum species were investigated by 27Al NMR spectroscopy and the tridecameric polycation Al 13 was detected. With the increase of PAC′s basicity, the molar ratio of Al 13 to Al m in PAC increases. The jar tests with kaolin water and water from Huangpu River at the same PACs dosage showed that the more basicity and content of Al 13, the more effective the coagulation effect on water with middle-high turbidity, while only less effect of the basicity was observed on water with low turbidity.