The solid state interactions occurring at high temperature in the Cr–FeB and Fe–CrB systems were studied by transmission Mössbauer and X-ray diffraction techniques on samples prepared by powders carefully mixed, cold-compacted and then treated at 1000°C for times up to 16 h. In the Cr–FeB system, iron atoms liberated by the substitutional diffusion of Cr into FeB lattice preferentially destabilize the iron monoboride with formation of Cr-containing Fe2B. In the Fe–CrB system, chromium atoms liberated by the substitutional diffusion of Fe into CrB lattice interacts with iron forming an Fe–Cr metal alloy. Moreover, zones of Cr-containing FeB and Fe2B form at the contact between metal iron and chromium monoboride, and tend to disappear as iron is consumed by the alloying process.