Abstract The effects of the incorporation of small amounts of Sn, Mn and Sm (0.5 at.%) on the structure and transport properties of glassy As2Se3 have been investigated. The metals influence both the disordered network structure of the glass matrix and the transport properties in accordance with the chemical properties of the doping elements. On metal addition, the electrical conductivity increases while the photoconductivity decreases. For Sm-modified glass, the position of the characteristic photoconduction band shifts toward higher photon energy. For Sn, the band shift is almost negligible and, for the addition of Mn, a photoresponse was not detected.