The invention provides a method for separating enriched palladium from a waste Pd/Al2O3 catalyst chloride leaching solution. The method mainly comprises the steps of adjusting pH in advance, performing sulfide precipitation, and acidizing to remove impurities. A waste Pd/Al2O3 catalyst is chloridized and dissolved so as to obtain a leaching solution, firstly, a NaOH solution is added, so that Al<3+> in the leaching solution exists in forms of meta-aluminic acid radical ions, other alkali metal ions are precipitated in the form of hydroxide, then a Na2S solution is added, so that [PdCl4]<2> in the leaching solution is converted into PdS, and finally, hydrochloric acid is added, so that the hydroxide is dissolved, and palladium sulfide is effectively separated from alkali metal impurities. The palladium recovery rate reaches 100%, and the purity is more than 95%. The method has the advantages of good selectivity, simplicity in operation, high enrichment efficiency, economy and environmental friendliness, toxic gas H2S cannot be generated, additionally, aluminum and palladium can be recycled, and the method is suitable for mass production.