We have studied the phase composition of the overlayer of scale which forms on TiFe at 700°C and 900°C (τ=5 h) by x-ray and metallographic analysis. The upper layers of the scale were shown to consist of TiO2 and Fe2O3 after heat treatment at 700°C, but the lower layers contain mainly TiO2, FeO, and Fe. The underlayer on the boundary with the scale contains Ti4Fe2O (η-phase). The inert marker is covered with rutile at 900°C, and FeTiO3 + TiO2 is below the marker. But the next (relatively thick) internal layer consists of FeTiO3, TiO2, and Fe. Large pores associated with intensive growth of the FeO phase are detected in the scale formed at 700°C. As a result, the scale cracks. At 900°C, the scale is denser because the pores and cracks are covered by rutile. We have shown that FeO (p-type semiconductor) is nonstoichiometric in the upper layers of the scale, and TiO2 (n-type semiconductor) is nonstoichiometric close to the boundary with the alloy. The results obtained correlate with the results for the oxidation kinetics previously studied for FeTi, and support a change in the oxidation mechanism when the temperature increases from 700°C to 900°C. Such a change occurs because of the influence of diffusion of the metal ion on oxygen diffusion through the boundary between the scale and the alloy: diffusion of iron through the vacancies in the FeO lattice at 700°C, and interstitial diffusion of titanium ions in the TiO2 lattice at 900°C.