<p>Ethylene glycol (EG) is the simplest diol, and its efficient conversion into high-value-added products is of great significance. In this work, a series of NiCuCeAlO_x catalysts with different Ni/Cu ratios and Ce contents were prepared by co-precipitation method, and were used to catalyze the reductive amination of EG to produce high value-added piperazine (PIP) and co-produce ethylenediamine (EDA) after reduction. The results demonstrate that under the optimal preparation conditions the EG conversion of 89.38% was achieved, and the PIP selectivity was 82.73%, with the total selectivity toward PIP and EDA of 92.6%. Compared to the Ce-free catalyst, the PIP selectivity increased by 15.7%, and the overall selectivity was enhanced by 16.6%. The results of Characterizations revealed that the incorporation of Ce improved the dispersion of Ni and Cu species on the alumina support, promoting the formation of Ni–Cu smaller particles with sizes ranging from 4 to 5&#xa0;nm. H₂-TPR and XPS results indicated that Ce exists in mixed + 3/ + 4 valence states, which significantly enhances the reducibility of Ni and Cu species on the alumina support. This promotes a higher proportion of surface Ni⁰ and increases the concentration of oxygen vacancies, which are identified as the key factors for achieving high PIP selectivity. Moreover, the catalyst maintained stable performance over four consecutive reaction cycles, demonstrating excellent reusability.</p> Graphical Abstract <p></p>