The invention relates to a catalyst for preparing ethanol by acetate hydrogenation as well as a preparation method and application of the catalyst. The catalyst comprises a mesoporous silica molecular sieve, an active copper component, and an oxide assistant of one or two elements of La and Ce. The catalyst comprises the following components in percentage by weight: 50-90% of silicon oxide, 10-50% of active copper component, and 0.1-20% of assistant. The preparation method of the catalyst combines a unique structure in the mesoporous molecular sieve MCM-41 forming process, a stilling ammonia precipitation-crystallization method is adopted to prepare a high dispersion copper-based and silicon-based catalyst, and the catalyst is favorable for enhancing the dispersion degree of the copper, and is suitable for forming the valence state distribution of the copper. The catalyst provided by the invention is used in the reaction of preparing ethanol by acetate hydrogenation, the conversion ratio of acetate is 98.5%, and the ethanol selectivity is 99.6%, and the hydrogenation activity, selectivity and stability are extremely high.