The aim of this study is to clarify the alpha-case formation mechanisms for the economic net-shape forming of Ti and Ti alloys. The α-case formation reaction between Ti and Al2O3 mold was examined in a plasma arc melting furnace. The reaction products were characterized by using an electron probe micro-analyzer and transmission electron microscopy. The α-case generation between Ti and Al2O3 mold could not be explained by the conventional α-case formation mechanism, which is known to be formed by the interstitials, especially oxygen dissolved from mold materials. However, on the basis of our experimental results and thermodynamic consideration, it was confirmed that the α-case is formed not only by interstitial oxygen atoms but also by substitutional metal atoms dissolved from mold materials. Based on the α-case formation mechanism, α-case free net-shape forming of Ti and Ti alloys could be possible for biomedical applications.