Current treatment processes for the cold rolling emulsion wastewater were in the dilemma that the cost was so high while the efficiency was not satisfied in China. In this work, a novel material with high-performance demulsification was obtained and used to treat the emulsion wastewater efficiently by modifying blast furnace dust (BFD), a steel industry waste. Firstly, the BFD was characterized by various analytical techniques and the results suggested that hydrophobic functional groups, positively charged iron oxide, and polysilicon in the BFD were contributed to removing stable oil droplets. Therefore, the BFD modification was conducted accordingly by optimizing the proportion and reaction conditions of these three components. The study demonstrated that the removal rate of oil and CODcr reached 75.21% and 81.23% under the conditions of the carbon type of GWF-HAC-R90, the carbon content of 14.86%, and the n(Fe)/n(Si) of 1.55, respectively. Based on this, the effects of pH, demulsifier dosage, and average agitation rate were investigated. The emulsion components before and after demulsification were analyzed by GC-MS, and the demulsification mechanism was expounded combined with kinetics. Results showed that the Fe2O3 with positive charge played a dominant role in emulsions with mainly anionic surfactants, while hydrophobic carbon structures and polysilicate acted as the auxiliaries. Besides, comprehensive analysis and characterization results suggested that the demulsification effect was a combination of the synergic processes: 1) electrostatic interaction developed by the anionic surfactant oil droplets and the positively charged the BFD particles; 2) hydrophobic association among the oil droplet with nonionic surfactant and amphiphilic carbon-iron complexes; 3) adsorption bridging between the surfactant oil droplets and polysilicate. The results of comparative tests in treating the actual cold-rolling emulsion wastewater showed the MBFD could bring about significant technical, economic benefits and achieve utilization of metallurgical solid wastes.Implications: Blast furnace dust (BFD) is an industrial solid waste obtained by dry de-dusting from blast furnace gas during the blast furnace ironmaking process. The main components of BFD are iron oxide and carbon, and also contain small amounts of different recoverable non-ferrous metals zinc, secret, indium and lead, which have recovery value. In this study, we enhanced the three parts of BFD and used to demulsification. In this study, the BFD was modified in three aspects (hydrophobic functional groups, positively charged iron oxide, and polysilicon) to achieve the secondary utilization of waste in emulsion wastewater treatment. And investigated the effect of reaction conditions on the demulsification effect with modified blast furnace dust (MBFD). Furthermore, the GC-MS analyzes combined with kinetics interpret the demulsification mechanism with the MBFD as a secondary resource. Finally, the comparative tests in treating the actual cold-rolling emulsion wastewater showed the MBFD could bring about significant technical and economic benefits and achieve utilization of metallurgical solid wastes.