The interactions of CP-Ti and Ti-6Al-4V with investment molds containing alumina/silica and yttria/silica face coat systems were studied. “Containerless” melting in argon was employed and small test samples were made by drop casting into the molds. The effects of the face coat material and mold preheat temperatures on the thickness of the alpha case in the drop castings were evaluated with microhardness and microprobe measurements. It was found that the thickness of the alpha case was the same, whether a yttria/silica or alumina/silica face coat was used, indicating that the silica binder can reduce the apparent inertness of a more stable refractory, such as yttria. It was also found that the alloyed titanium castings had a thinner alpha case than those produced from CP-Ti, which suggests that the thickness of the alpha case depends on the crystal structure of the alloy during cooling from high temperatures. Furthermore, the small drop castings made in small yttria crucibles used as molds exhibited little or no alpha case.