The effect of CuO on the clinkering process and mineral structure, components and morphology of high C 3 S cement clinker was studied. One reference mixture was prepared according to the potential mineral phase components C 3 S=75%, C 3 A=7%, C 4 AF=18% and then was mixed, respectively, with 0.5%, 1%, 1.5%, 2%, 2.5% and 4% CuO. All samples were heated at a rate of 10°C/min to the design temperatures and then maintained for 40 min. Analyses by the glycerol-ethanol method, XRD and SEM-EDS show that the minimum of free lime (f-CaO) content was related to temperature and CuO amount. The higher the temperature, the lower the amount of CuO corresponding to the f-CaO minimum content. CuO promotes the formation and growth of C 3 S and C 4 AF and a new compound is found. In addition, these phenomena are discussed theoretically. In conclusion, CuO alters the burnability and the formation and structure of C 3 S in a high C 3 S cement system.