The invention relates to a preparation process of using industrial slag to prepare composite cementing materials with high expansibility. The cementing materials consist of four components. The first component includes three parts: one or a plurality of combinations of fly ashes, slag, etc., which contain aluminosilicate; one or a plurality of combinations of phosphogysum, fluorine gypsum, etc., which contain calcium sulfate; one or a plurality of combinations of carbide, alkaline residue, quick lime or slaked lime. The second component includes: one or a plurality of combinations of alkaline composition, such as the quick lime or slaked lime, the carbide slag, etc.. The third component includes one or a plurality of combinations of the phosphogypsum, fluorine gypsum, etc., which contain the calcium sulfate. The preparation method is: firstly, to evenly mix the raw materials of the first component which are grinded to be with the surface area of 200-500m<2> / kg through the steam curing of four hours to ten days at 50-100 DEG C and the calcining of 0.5-24h at the high temperature of 400-1000 DEG C to obtain the first component; secondly, to dry and grind the raw materials of the second and the third component to be with the surface area of 200-500m<2> / kg to obtain the second and the third component; thirdly, to evenly mix the first, the second and the third component.