An integrated sodium roasting-reductive leaching process was developed to recover Pd and Al₂O₃ from spent Pd/Al₂O₃ catalyst. The thermodynamic analysis of sodium roasting indicated that NaOH, Na₂CO₃ and Na₂C₂O₄ could completely react with Al₂O₃ to form NaAlO₂ at the optimal Na₂O/Al₂O₃ molar ratio and temperature. The Al₂O₃ leaching ratios were 99.6%, 61.0% and 55.3%, respectively, when the roasted residues from NaOH, Na₂CO₃ and Na₂C₂O₄ roasting were subjected to water leaching. Mechanical activation-dry NaOH roasting process avoided the consolidation of roasted residue, and high Al₂O₃ leaching ratio could be obtained. Reductive leaching with N₂H₄·H₂O averted Pd dissolution loss during water leaching, and 99.7% of Al₂O₃ in the catalyst was leached. NaAlO₂ leachate and Pd-enriched residue were finally obtained, and the valuable Al and Pd can be further recovered.