The use of dolomite refractories has increased during the past several years in the manufacturing of clean steel during the stainless steelmaking process. However, at the same time, the use of dolomite refractories has led to what is known as the skull formation. In the present work, to understand the skull formation, the wetting characteristics of dolomite substrates by liquid Fe-19wt%Cr-10wt%Ni alloys in various oxygen partial pressures were initially investigated at 1753K using the sessile drop technique. For comparison, the wetting characteristics of alumina substrates were investigated with the same technique. It was found that the wetting index, (1+cosθ), of dolomite is approximately 40% higher compared to those of alumina. In addition, the oxygen partial pressure to generate the surface oxide, which may capture the liquid metal on the refractory surface, for dolomite is much lower than that for alumina. From this study, it was concluded that the use of dolomite is much more closely associated with the skull formation compared to the use of alumina due to the stronger wettability and the surface oxide formation at a lower oxygen partial pressure of dolomite.