The matching of hydrogenation sites and acid sites is the key to design efficient catalyst for the synthesis of cyclopentanone from lignocellulosic derived furfural. In this work, Co-Ni/Nb2O5 catalyst with three-dimensional open flower cluster structure was constructed. The results of characterization and theoretical calculation show that the introduction of Ni leads to the formation of Co-Ni alloy, tailoring the electronic properties of metal center and acidity of the catalyst. On the one hand, it effectively enhances the activation of H2, modulates the d-band structure of the metal center, thus controlling the adsorption configuration of the substrate, leading to the selective activation of carbonyl groups and avoiding the furan hydrogenation byproduct. On the other hand, it promotes the ring-opening rearrangement of intermediates. Benefiting from the synergistic effect of hydrogenation sites and acidic sites, 99.0 % yield of CPO was achieved under mild conditions (150 ℃ and 1.5 MPa for 4 h) within 6 cycles. Therefore, this study will provide a new way to realize the green manufacturing of cyclopentanone.