The present study describes refractories which contribute to formation of skin holes of Ti casting. Plates consisting of quartz (Qu) and cristobalite (Cr) powders and Qu- and Cr-MgO mixtures were fired at high temperatures and used as phosphate-free molds. The cross-section of the castings was investigated using an optical microscope and an electron probe microanalyzer. Whereas the castings into the Qu molds were almost complete, those into the Cr molds were incomplete. The surface reaction zone of the Qu molds formed a typical layered structure with fewer skin holes. That of the latter extended deeply into the interior with a net-shaped Ti-Si phase, cracks, and holes. Addition of MgO to Cr effectively improved the castability and changed the reaction zone to the typical layered structure. However, slender holes occurred along the mold wall. The overall area around the holes was contaminated by Si and Mg. Probably, this resulted from a reaction of forsterite with Ti. The reactivity difference between Qu and Cr was not related to the fired strength of mold.