Electronic structure and photoelectrical properties of VO₂, such as dielectric constant, absorption constant, refractive index, and conductance are studied with SCC-DV-Xα-ECM method. A broad band, in the upper part of which Fermi energy level is located, is formed by combination of 2p energy band of O and 3d energy band of V. VO₂ exhibits metal characteristics. The peak around 0.8 eV is dominated by electronic intraband transition and the peak between 5~7 eV is mainly dominated by electronic band-to-band transition. The refractive index and extinction coefficients calculated consist with experimental results.