The surface oxidation and wettability of Mn and Si-alloyed steel after annealing at different conditions are studied with scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and a so-called de-wetting method. After exposure at 950 °C for 1 hour in an Ar + 5 vol pct H₂ gas atmosphere with dew points (DP) ranging from – 40 °C to 10 °C, oxides were observed along the grain boundaries or dispersed on the surface for the Fe–1.8 Mn steels while a continuous oxides layer was formed on Fe–1.9 Mn–0.94 Si steels (composition in weight fractions). The oxides formed at different DPs were predicted based on thermodynamic calculations. (Fe,Mn)O was formed on Fe–1.8 Mn steel at the whole range of DPs, while the oxide phase on Fe–1.9 Mn–0.94 Si steel depends on the DP. At low-DP SiO₂ were formed and with increasing the DP (Fe,Mn)SiO₃ or (Fe,Mn)SiO₃ + (Fe,Mn)₂SiO₄ were formed and finally (Fe,Mn)₂SiO₄ were formed. An increase of the fraction of Fe in the oxide with increasing DP for both steels was observed with XPS analysis. As a measure for the surface wettability, the contact angle of Pb droplets on the annealed steels surfaces was determined with SEM and image analysis software. Also, the contact angle of Pb on pure Fe and on the Mn and Si alloyed steels free of surface oxides was measured for comparison. The results show that the contact angle of Pb on the steel surfaces after annealing decreases with increasing DP. This improved wettability with increasing dew point is related to the Fe fraction of the oxides formed on the surface.