Auto-catalysts were the largest consumers of platinum group metals and the most important secondary resources, recovery of PGMs from spent auto-catalysts by leaching with various acidities were investigated. The leaching thermodynamics of PGMs at 363 K was first discussed. At 363 K the higher the acidities of HCl, the higher the leaching recoveries of PGMs, and the sequence of leaching recovery was PdPtRh. When H2SO4 used alone, the leaching recoveries of PGMs was low, when the acidity of H2SO4 increasing, the leaching recovery of Rh kept stable.