Disclosed are a molybdenum based composite oxide catalyst, its preparation method and use. The catalyst has the following general formula: BiMoxMyNzOa; wherein M is one of V, Cr, Mn, Fe, Co, Ni and Cu, or a mixture of two or more of V, Cr, Mn, Fe, Co, Ni and Cu in any ratio; N is one of Na, K, Cs, Ca and Ba, or a mixture of two or more of Na, K, Cs, Ca and Ba in any ratio; x=0.5˜20; y=0.05˜20; z=0.01˜5; a is a number satisfying the valance of each atom. The catalyst is prepared by the following method: firstly mixing a certain amount of the lead metal oxides according to the chemical proportion and then grinding the mixture with high-energy ball milling for a period of time to obtain the molybdenum based composite oxide catalyst. The catalyst exhibits excellent performance when using for preparation of butadiene by oxidative dehydrogenation of butene, and the preparation process is simple, controllable, and repeatable. Waste water or waste gas that is difficult to be treated is not produced during preparation.