Utilizing the Maker fringe method, SHG was observed in the 0.95GeS2·0.05In2S3 chalcogenide glass irradiated by the electron beam and the intensity of SH increases with the enhancement of beam current from 15 to 25nA. According to Raman spectra of the as-prepared and the irradiated one, no distinct micro-structural transformation was found. In this work, the built-in charge model was founded to interpret the poling mechanism of electron beam irradiation, the emission of the secondary electrons and Auger electrons results in the formation of positive region and the absorbed electrons form negative region. The positive region was situated near the poling surface, and the negative region was much deeper than the positive region. Between the two opposite charged regions, a strong space-charge electrostatic field, Edc, is created, which leads to the nonzero χ(2) in the 0.95GeS2·0.05In2S3 glass. The emission of backscattered electrons does no contribution to the formation of Edc.