The effect of temperature, atmosphere, and elemental concentrations of boron and phosphorous in ferrous alloys on the wettability of polycrystalline α‐Al2O3 was studied. The investigation of the wetting behavior is of major importance to the infiltration of steel into open foam ceramics. In reference Fe‐0.46 wt% C iron samples, the contact angle was investigated between 1550 and 1650 °C under Ar‐H2 and Ar atmospheres and was found to decrease with increasing temperature and increasing oxygen partial pressure. Furthermore, no FeAl2O4 (hercynite) spinel type inclusions were found in Fe/Al2O3 experiments. In the Fe‐P binary alloys, θ decreased with increasing phosphorous content and was ≈112° for the Fe‐0.299 wt% P alloy at 1600 °C. For the Fe‐B binary alloys, a strong influence of boron on the contact angle was found. Secondary neutral mass spectrometry (SNMS) analysis showed a maximum in the boron concentration in the first 50 nm of the metallic side of the interface. In the FeCrMnNi‐P high‐alloys specimens, a reaction layer was found between the steel/ceramic interfaces. The contact angle was ca. 90°, lower than the Fe‐P binary alloys.