The wetting behavior of liquid iron and steel on Al₂O₃, MgO and Ti₂O₃ substrates was measured by using the sessile drop method. Measurements were carried out using a controlled oxygen partial pressure and using an argon protected atmosphere. For the Al₂O₃ and MgO substrates, reaction layers in form of FeAl₂O₄ and MgO–FeO (solid solution) were formed. These layers slightly decreased the contact angle and surface tension values after a full melting. For a Ti₂O₃ substrate in contact with pure Fe, no-reaction could be observed at the interface. Furthermore, the contact angle and surface tension values were almost stable after a full melting. For a Ti₂O₃ substrate in contact with steel, the contact angle and surface tension values decreased steeply after a full melting, due to the formation Al₂TiO₅ reaction layer formation at the interface.