The recovery of platinum group metals (PGMs) from waste materials involves dissolving the waste in an aqueous solution. However, since PGMs are precious metals, their dissolution requires strong oxidizing agents such as chlorine gas and aqua regia. In this study, we aimed to recover PGMs via the calcination of spent automotive catalysts (autocatalysts) with Li salts based on the concept of “spent autocatalyst + waste lithium-ion batteries” and leaching with only HCl. The results suggest that, when Li2CO3 was used, the Pt content was fully leached, while 94.9% and 97.5% of Rh and Pd, respectively, were leached using HCl addition. Even when LiF, which is a decomposition product of the electrolytic solution (LiPF6), was used as the Li salt model, the PGM leaching rate did not significantly change. In addition, we studied the immobilization of fluorine on cordierite (2MgO·2Al2O3·5SiO2), which is a matrix component of autocatalysts. Through the calcination of LiF in the presence of cordierite, we found that cordierite thermally decomposed, and fluorine was immobilized as MgF2.