Mesoporous structured Ni(10 wt%)/CeO2, prepared via a simple incipient wetness impregnation of mesoporous CeO2, was used as a novel catalyst for the maleic anhydride hydrogenation (MAH) and characterised using XRD, N2 adsorption–desorption, H2-TPR, XPS and H2-TPD techniques. In comparison with the Ni(10 wt%)/Al2O3, the Ni/CeO2 exhibited nearly 12 times higher initial specific activity in MAH than in succinic anhydride (SA) and enhanced selectivity to γ-butyrolactone (GBL) in the subsequent hydrogenation process. The two-step route of MAH on Ni/CeO2 was verified based on the faster conversion rate of maleic anhydride (MA) to SA, in which Ni determines initial selectivity while CeO2 can promote the conversion rate. The excellent catalytic performance of the Ni/CeO2 was related to the higher dispersion of metallic Ni, oxygen vacancies on the CeO2 support and the suitable porosity of the Ni/CeO2.