The electronic structure of α2-Ti3Al (0001) surface was calculated by the first principle based on density functional theory. The results show that: (1)the surface energy of the α2-Ti3Al (0001) surface is 2.03 J/m2, and the surface work function is 4.265 eV; (2)the total density of states on the surface reaches a maximum value at the Fermi level, and the system exhibits a metallic property, which is significantly different from the semimetal of the α2-Ti3Al bulk, Ti-s, Ti-p and Al-s orbitals are less affected by the number of layers, while Ti-d and Al-p orbitals are more affected by the number of layers, and all of them have maximum values at the Fermi level; (3)the nodal line ring is not present in the band structure of the surface, but there is a three electronlike bands crossing point at Γ point under the Fermi level, and there is a two holelike bands crossing point at Γ point above the Fermi level.