1,5‐dimethyl‐2‐pyrrolidone (MNMP), as a highly efficient green solvent, can be obtained from biomass‐derived levulinic acid and its esters with 100% conversion and 96.8% yield over a 10% Ni@CeOx catalyst at 140 °C, 2 MPa H2, 8 h, and with water as the solvent. Structure‐property correlation investigations were performed with diverse characterization methods, including BET, XRD, XPS, TEM, HAADF‐STEM, H2‐TPR, NH3‐TPD, CO2‐TPD and FT‐IR, and the results revealed that the excellent catalytic performance of the 10% Ni@CeOx catalyst was mainly resulted from the strong interaction between Ni and CeOx, which formed more catalytic active sites and contributed to higher reductive amination efficiency. Besides, the 10% Ni@CeOx catalyst had a chemisorption effect on LA. This was also the key to the excellent catalytic activity of the 10% Ni@CeOx catalyst. The 10% Ni@CeOx catalyst exhibited great stability throughout 6 reaction runs and excellent catalytic efficiency in the kilogram scale preparation of MNMP. This work provides a low‐cost, efficient, and environmentally friendly heterogeneous catalytic system for the production of MNMP.