In order to study the optical properties of the PWO crystal containing V2-Pb, the optimization of the lattice structure containing V2-Pb has been performed by using LAPW+lo method and the conjugate gradient method. All other calculations are performed on the basis of the lattice structure being optimized. The electronic structure, dielectric function, complex refractive index and absorption spectra for the perfect PbWO4(PWO) crystal and the PWO crystal containing V2-Pb have been calculated by using LAPW+lo method. The peaks of the absorption spectra corresponding which electronic transitions have been studied. The calculated results indicate that the perfect PWO crystal does not have absorption band in the visible and near-ultraviolet region; however, the PWO crystal containing V2-Pb has two absorption bands in this region. The two absorption bands can be well fitted into four Gaussian-shape bands peaking at 350 nm, 405 nm, 550 nm and 670 nm. This predicates that the 350 nm, 420 nm, 550 nm and 670 nm absorption bands are related to the existence of the V2-Pb in PWO crystal.