The coalloying with high contents of chromium (Cr), boron (B) and yttrium (Y) for porous B2-structured FeAl intermetallics fabricated through reactive synthesis was conducted. The oxidation behaviors of porous FeAl-based materials were investigated by evaluating the pore-structure evolution, oxidation kinetics and oxide-scale configuration. The results show that with the coalloying of high contents of Cr, B and Y, the oxidation mass gains of porous FeAl materials at 600-800 °C are significantly reduced. The combination of B enriched on the surface of oxide scales and Y located at the scale-metal interface promotes the formation of thin protective nodular α-Al₂O₃ oxide scales. It is indicated that introducing relatively high contents of reactive elements such as B and Y can benefit the selective growth of α-Al₂O₃ scales at relatively low temperatures without pre-treatment.