This paper presents the results of investigation of four cast alloys based on the Fe3Al intermetallic phase. Microstructure tests using light microscopy, electron scanning microscopy and X-ray diffraction methods, have been performed. On this basis, a presence of particles rich in zirconium and molybdenum, and in case of the alloy with 28 at.% aluminium and 5 at.% chromium — the presence of sigma phase (FeCr), has been found. Also, the results of the study of the microstructure influence on the electrochemical corrosion resistance in the 5 % NaCl solution have been presented. The Fe-26Al-2Cr-1Mo-0.1Zr-0.005B at.% and Fe-26Al-5Cr-1Mo-0.1Zr-0.005B at.% alloys exhibited increased corrosion resistance in comparison to the Fe-23Al-1Mo-0.1Zr-0.005B at.% alloy without chromium addition. The appearance of the sigma phase in the alloy of Fe-28Al-5Cr-1Mo-0.1Zr-0.005B at.% chemical composition resulted in lowering the corrosion resistance of this alloy and a change in corrosion character from the pitting to the intercrystalline one.