Currently, highly efficient biomass upgrading over non-noble metal catalysts is of vital importance for reducing equipment and operation expenses in biorefinery industries. In this respect, the related heterogeneous catalysis demands the design and construction of mutual cooperative microstructure of catalysts to improve their catalytic performances. Here, an efficient catalytic process for selective hydrogenolysis of biomass-derived gamma-valerolactone (GVL) to produce 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF) was developed by earth-abundant nickel-based catalysts, which were derived from a molybdate intercalated Ni-Al layered double hydroxide precursor. It was found that with the elevated reduction temperature, the amount of surface defective MoOx species (0 < x < 3) was gradually increased. Especially, as-fabricated Ni-MoOx/Al2O3 catalyst obtained at the reduction temperature of 600 degrees C delivered a 94.0% combined yield of 1,4-PDO and 2-MTHF under mild reaction conditions. It was demonstrated that over the present Ni-MoOx/Al2O3 catalyst system, surface defective MoOx species could greatly facilitate the adsorption and activation of carbonyl group in GVL and thus significantly promote the cleavage of C=O bond and its adjacent C-O bond. This finding opens a promising door to engineer surface defective structure of high-performance supported metal catalysts. (C) 2019 Elsevier Inc. All rights reserved.