This review is concerned with the effect of the addition of zirconium as a third element on the heat-resisting properties of Fe3Al intermetallic compounds and explains their high-temperature oxidation mechanism. The Fe3Al and Fe3Al-0.05Zr specimens were isothermally oxidized in the temperature range of 1173～1473 K in synthetic air for 100 h. The formation of the alumina layer approximately obeyed the parabolic rate law, with the exception of short initial stage. The parabolic rate constant values for the Zr-doped Fe3Al decreased at all tested temperatures. Fe3Al revealed massive spallation, whereas Fe3Al-Zr produced a fiat, adherent oxide layer. The microstructure investigations of the alumina scales grown thermally on the Fe3Al-Zr alloy by means of SEM-EDS showed that they were 1.5～2 μm thick and consisted of a small inner columnar layer and an equiaxed outer grain layer. Additionally, very fine (50～150 um) oxide particles rich in Zr were found across the alumina scales. The addition of Zr significantly affected the oxidation behavior of Fe3Al by improving the adherence of the α-Al2O3 scale. TEM-SAD investigations of the alumina scales on samples prepared using the FIB (Focused Ion Beam) method confirmed the presence of small tetragonal zirconia grains near the scale/gas and alloy/scale interfaces, most of which were formed along alumina grain boundaries(gbs). Zr gb-segregation was found using HRTEM. The role of preferential formation of zirconium oxide along the alumina scale grain boundaries and the effect of Zr gb-segregation on oxidation and scale growth mechanisms were analyzed by means of two-stage oxidation experiments using 16O2/18O2. The SIMS oxygen isotope profiles for the Fe3Al-Zr alloy oxidized at 1373 K, after two-stage oxidation experiments, revealed that oxygen anion diffusion is predominant compared to that of aluminum cation diffusion.