The conventional biological treatment technology is inefficiently for coking wastewater. It is meaningful to study the advanced treatment process for these kinds of wastewater. A new compound montmorillonite adsorb-coagulant was prepared by complex formulation of microwave organic modified montmorillonite, Na- montmorillonite and polyaluminium chloride (PAC). And it was used in the advanced treatment of coking wastewater after biological treatment. Experimental results show that the mass ratio of microwave organic modified montmorillonite, Na-montmorillonite and polyaluminium chloride (PAC) is 20: 20: 1, and under the condition of the dosage of 30 g/L, the adsorb-coagulation time of 30 minutes and the sedimentation time of 2 hours, the treatment effect is the best. The effluent concentration of COD and ammonia nitrogen is 33.6mg/L and 10.1mg/L, respectively, and the chroma of effluent is only 2 time. The corresponding removal efficiency is 78.2%, 84.8% and 92%, respectively. And the out-effluent can completely reach the first national discharge standard.