Aqueous-phase hydrogenation-rearrangement tandem (AP-HRT) reaction is a green and sustainable route to produce cyclopentanone from bio-based furan compounds. Herein, the ionic liquid was applied as the precursor to synthesize Ni@NP-C catalyst, which contains high dispersed nickel nanoparticles (Ni NPs) encapsulated in the N, P co-doped carbon layer, for the selectivity transformation of furfural towards cyclopentanone. The synthesized Ni@NP-C catalyst can afford 100% FAL conversion and 86.7% CPO yield at 130 °C and 1.5 MPa H2 within 2 h AP-HRT reaction. The introduction of the electronegative heteroatom on the surface can not only improve the adsorption of reactant but also provide weak Lewis Acid sites for being beneficial to the high selectivity of cyclopentanone. The catalyst displays superior activity, selectivity, and stability in the tandem catalytic system in view of the tunable chemical states of the doped heteroatoms by handily adjusting the pyrolysis temperature.