The invention belongs to the technical field of catalysis, and relates to a preparation method of a catalyst for hexone synthesis by acetone hydrogenation and an application; the catalyst is composed of active component nickel loaded on an alumina carrier modified by transition metal oxides. The preparation method of the catalyst comprises two procedures: the first one is that transition metal oxides and alumina are mixed, molded, dried, roasted, and subject to hydro-thermal treatment, and the active component Ni is immersed to obtain the catalyst; the second one is that an alumina carrier is prepared firstly, then transition metal oxides and Ni are introduced by an immersion method, and finally hydro-thermal treatment is performed to obtain the catalyst. The catalyst of the invention adopts non-noble metal as the main active component, is simple in preparation, low in cost, strong in raw material adaptability, long in service life, and high in activity and selectivity, and combines three catalytic functions of acetone condensation, dehydration, and hydrogenation as a whole, and the reaction process flow is simplified greatly.