Gamma alumina is widely utilized for preparing the supported noble metal catalysts for the hydrogenation reaction. It is an effective strategy to improve the catalytic performance of catalysts via modifying gamma alumina with alkaline earth metal to regulate its surface acidity and electronic properties. Herein, Pd catalysts supported by Al₂O₃ and Mg-modified Al₂O₃ are synthesized via the wet impregnation method, and the effects of MgO doping on the structure, composition, and surface acidity of Pd/γ-Al₂O₃ catalysts are investigated via X-ray diffraction patterns (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Temperature programmed desorption (TPD). The results show that Pd/MgO-Al₂O₃–2 (γ-Al₂O₃ modified with 2 wt% Mg) has more metallic state palladium and weak acid sites and exhibits the best catalytic performance for the hydrogenation of perfluoro-4-methyl-2-pentene (D1). Density functional theory (DFT) calculations on Pd/Al₂O₃ and Pd/MgO-Al₂O₃–2 catalysts are also performed to further explore the mechanism of D1 hydrogenation. The studies for Gibbs free energy of the potential reaction steps and intermediates reveal a complex process to generate the target product C₆F₁₂H₂, and the rate-determining-step is the addition of the first hydrogen on the second carbon of perfluoro-4-methyl-2-pentene molecule.