The invention relates to a method for separating enriched palladium by adopting supermolecule secondary spherical coordination identification. The method adopts the technical scheme as follows: taking a certain amount of sample solution containing palladium, adding an alcoholic solution of protonized dibenzyl amine to the sample solution containing palladium, adding acid to the mixture, standing the new mixture for 5 hours to 24 hours, filtering the new mixture to obtain solid complexes, drying the obtained solid complexes, dissolving the obtained solid complexes with ammonia, extracting the obtained solid complexes with inert organic solvent to separate organic phases; and taking a water phase as a solution for extracting the palladium, wherein the alcoholic solution can be ethanol, tert-butyl alcohol, n-propanol, isopropyl alcohol, carbinol, n-butyl alcohol, isobutyl alcohol or glycol, the acid can be hydrochloric acid, sulphuric acid, nitric acid, acetic acid, p-toluene sulfonic acid, benzene sulfonic acid and trifluoroacetic acid or the mixture of some of the same, and the inert organic solvent can be nitrobenzene, bromobenzene, chlorobenzene, petroleum ether, chloroform, paraffinic oil, coal oil, methylene dichloride, benzene, toluene or dimethylbenzene or the mixture of some of the same. With the method, the palladium can be rapidly separated from other base metals with high efficiency and high selectivity.