The invention provides a method for preparation of 1,4-pentanediol and 2-methyltetrahydrofuran by high-selectivity hydrogenation of gamma-valerolactone, specifically to preparation and application for a supported non-noble metal Cu/Ni catalyst by using perovskite as a carrier. The catalyst of the invention realizes preparation of 1,4-pentanediol and 2-methyltetrahydrofuran by catalytic hydrogenation of gamma-valerolactone with high efficiency, and the reaction is conducted in a continuous stirred tank reactora continuous batch reactor and a continuous fixed bed reactor. The catalyst has high activity, high selectivity and high stability, and the target products can be controlled with high selectivity by changing reaction conditions. The reaction conditions are mild, the process is simple, and the method has a good prospect of industrial application.