Based on the density functional theory, the change of structure, energy band, conductivity, reflectivity and absorptivity of V-TiO2 of different concentration were investigated by first principle calculation. Intrinsic doping model of TiO2 and VxTi1-xO2(x=0.062 5, 0.125, 0.187 5)was established and the doping system is higher in conductivity with characteristics of N-type semiconductors. BP neural network was adopted to train the energy band results of the intrinsic doping model, and the data results of training model show that higher conductivity was achieved after doping and the energy gap was significantly reduced. Considering the above results, optimal conductivity and optical performance can be achieved when x=0.187 5.