γ-valerolactone (GVL) is an important value-added chemical with potential applications as a fuel additive, a precursor for valuable chemicals, and polymer synthesis. Herein, different monometallic and bimetallic catalysts supported on γ-Al₂O₃ nanofibers (Ni, Cu, Co, Ni-Cu, Ni-Co, Cu-Co) were prepared by the incipient wetness impregnation method and employed in the solvent-free hydrogenation of levulinic acid (LA) to GVL. The influence of metal loading, metal combination, and ratio on the activity and selectivity of the catalysts was investigated. XRD, SEM-EDS, TEM, H₂-TPR, XPS, NH₃-TPD, and N₂ adsorption were used to examine the structure and properties of the catalysts. In this study, GVL synthesis involves the single-step dehydration of LA to an intermediate, followed by hydrogenation of the intermediate to GVL. Ni-based catalysts were found to be highly active for the reaction. [2:1] Ni-Cu/Al₂O₃ catalyst showed 100.0% conversion of LA with >99.0% selectivity to GVL, whereas [2:1] Ni-Co/Al₂O₃ yielded 100.0% conversion of LA with 83.0% selectivity to GVL. Moreover, reaction parameters such as temperature, H₂ pressure, time, and catalyst loading were optimized to obtain the maximum GVL yield. The solvent-free hydrogenation process described in this study propels the future industrial production of GVL from LA.