The wetting characteristics of liquid iron on dense MgAION-based composite ceramics were investigated using X-ray sessile drop technique. The contact angles were measured on substrates of different composites as functions of temperature and varying partial pressures of oxygen. The results with pure argon gas showed that contact angles kept almost constant in the temperature range 1823 to 1873 K. The contact angle was found to show a slight increase with increasing boron nitride (BN) content in MgAION-BN composites. These are attributed to the higher contact angle between BN substrate and liquid iron drop compared with that obtained for MgAION substrate. When the CO-CO2-Ar gas mixtures were introduced into the system, the contact angle showed an initial quick decrease followed by a slow decrease and then a period of nearly constant contact angle at a given temperature corresponding to the steady-state condition. Even in this case, BN seemed to cause an increase in the equilibrium contact angle. The equilibrium contact angle was found to decrease with increasing temperature. XRD results indicated that the substrate was oxidized and the oxidation products combined with FeO formed by the oxidation of the iron drop to from FeAl2O4 and Mg1−xFex) These were likely to form a ternary FeO-Al2O3-MgO slag or a quaternary slag by combining with B2O3. An interesting observation is that the iron drop moved away from the original site, probably due to the Marangoni effect.