The current study investigated the microstructure evolution and anti-corrosion behavior of low Y doping alloys of Fe13Cr6Al(1–4)Mo0.15Y subjected to high-temperature steam (800 °C to 1300 °C). The results indicate that steam oxidation induces the growth of high-quality oxidation film that is thermodynamically driven, with rapid increases in the thickness from 800 °C to 1300 °C without film convolution and spallation. The film convolution and spallation were successfully suppressed through on-site formation of the high-temperature stable ternary crystalline phase (Y2Mo3O12) and decreasing of the thickness of α-Al2O3 oxidation film during the fabrication and oxidation scenario. The on-site steam oxidation rate has been significantly suppressed, with lower weight gain and less oxidizing film convolution than monolithic FeCrAlMo alloy, through the addition of a low concentration of Y.