The invention relates to a process for producing alcohol and selectively co-producing 2-butanol by hydrogenising acetate and a matching process system thereof. After industrial acetate is hydrogenised and purified, a product is rectified, purified and dehydrated, thereby obtaining alcohol and co-producing 2-butanol. Cu-Zn-M is taken as an active component of a catalyst adopted in the process, wherein M is selected from the compound of one and more of Ir, Mn, W, Ru and Zr. 2-butanol is selectively co-produced by adjusting the reaction temperature. The catalyst, process and device adopted by the invention have the characteristics of high activity, high selectivity, high yield, strong market adaptability, less equipment investment, environmental protection, simpleness in preparing process, economical and practical properties, and the like. Meanwhile, conversion per pass is high and reaction heat is effectively utilized, so that the load for separating rough products is greatly relieved, the production flow is shortened and the energy consumption of production is also greatly reduced.