A series of self-assembled Pd/CeO2 catalysts were synthesized by a facile one-pot redox method, demonstrating high catalytic performance in hydrogenation of levulinic acid. Under optimized conditions, almost 100% gamma-valerolactone yield was achieved using Pd/CeO2 catalyst with only slight activity loss (ca. 4%) after five continuous runs. Combined with relevant characterization techniques, the superior catalytic hydrogenation performance could be attributed to Pd/CeO2 catalyst with noticeable advantages of high surface area beneficial to the exposure of Pd catalytic active sites and increase electron density of Pd favorable for the dissociation of H2 as well as the defects sites of CeO2 responsible for esterification of intermediate.