An experimental study was conducted to investigate the interfacial phenomena between Al-alloy and industrial grade high alumina refractories containing varying contents of CaF 2 at 1250°C. Interfacial reaction products and phases formed in the heat-treated refractory samples were characterized using electron probe microanalysis (EPMA) and X-ray diffraction (XRD), respectively, while interfacial phenomena including dynamic wetting behavior were analyzed using the sessile drop technique. Refractories containing less than 5 wt pct CaF 2 showed good resistance to reactions with the molten alloy, due to the dominance of corundum, and the presence of anorthite at the interface. However, with a further increase in the additive content, a glassy matrix of anorthite with CaF 2 was formed. Formation of this phase significantly increased the intensity of reactions resulting in the buildup of an interfacial layer. The study thus revealed the strong catalytic effect of CaF 2 on reactions of high alumina refractories with Al-alloy.