Among platinum group metals (PGMs), Pt, Pd, and Rh are the essential constituents of automotive catalysts. Recovery of PGMs from catalyst scrap is important, but it is difficult because PGMs are chemically stable and are present as minor components in the scrap. In this study, the authors investigated the reaction between PGMs and FeCl2 vapor in order to develop a novel method for the separation and concentration of PGMs directly from catalyst scrap. The wire samples of Pt, Pd, and Rh were reacted with FeCl2 vapor in a steel vessel maintained at 1200 K. After the heat treatment, the surfaces of PGM wires were alloyed with Fe, and these samples became magnetized. The results obtained in this study suggest that a FeCl2 vapor treatment followed by magnetic separation can be utilized as an effective technique for the separation of PGMs directly from catalyst scrap.