The bulk of raw materials in metallurgy of secondary platinum metals are the wastes such as multilayered ceramic-metal systems, e.g. the spent catalysts of the chemical and petrochemical industry, automobile catalysts, etc. Due high chemical resistance of a ceramic basis the extraction of platinum metals by leaching even at very fine crushing is poor. The study of sorption leaching of platinum and a palladium from the spent automobile catalysts are carried out. The average content of PGM is 0.5%. A few methods of raw materials sampling were compared: 1) direct hydrometallurgical leaching of platinum metals from the fine-grained catalyst and atomic absorption analysis of the obtained solutions; 2) fusion to a metal or sulphidic collector of precious metals with the alloy analysis by direct spectrometry; 3) fusion with dissolution of a precious metals collector and atomic absorption analysis of PGM in solutions. Leaching allows detecting out no more than 90% of a palladium and 80% of platinum. Fusion to a collector gives the best results at the chemical ending. Researches on sorption leaching are executed. Under optimum conditions the extraction of platinum metals to concentrates is comparable with similar indicators of collector fusion.