In this paper, the electronic properties of silicon were studied by the first-principles methods at constant voltage. The research shown that the stress distribution along the crystal planes of (001), (101) and (111). The conduction band and valence band of Si shown anisotropy in the energy level and splitting energy at the G point of the band edge, sub band edge and secondary band edge. On the basis, we analyze the charge and bonding of Si material on [110], [101], [011], study the effect of changes in valence band structure on hole mobility, the results shown that the differential charge density is different on each surface, the intrinsic properties between the bonding method and the electronic structure. The calculation results provide data support and basis for the later research of silicon.