Coal gangue is a kind of waste from coal mine processing. Polyaluminium ferric chloride (PAFC), a new type of inorganic composite coagulant, was prepared by using the waste from the Mineral Bureau of Yanzhou, China, hydrochloric acid and calcium carbonate as raw materials. The relationship between the stability of ferric ion and the ionic strength of solution was investigated. The zeta potential of PAFC hydrolysis products of PAFC and the coagulation performances under different pH value were discussed. The turbidity removal properties of PAFC, polyaluminium (PAC) and polyferric sulfate (PFS) were compared, and the color removal effect of PAFC for the wastewater containing suspended dyes was also tested. In addition, the coagulation performance of PAFC for actual wastewaters from petrochemical plant, iron and steel plant, and coal mining processing was evaluated. The experimental results suggest that PAFC took a maximum value of zeta potential at about pH 5.8 on the positive side. Compared with PAC, PAFC gives better turbidity removal performance in the range of pH from 7.0 to 8.4. PAFC gives good color removal performance on suspension dyes. PAFC also gives good wastewater purifying results for the actual wastewater. Therefore, PAFC is a high-effect and stable water treatment agent.