The effect of low concentrations of two groups of doping impurities (one group includes Sn, Pb, Dy, Ho, Y and the other group includes In, Cs, and Al) on photoelectric properties of As₂Se₃ and (As ₂S₃)_0.3(As₂Se₃) _0.7 was investigated. Studies of spectral distributions of photoconductivity and optical absorption showed that there is a distinct increase in photoconductivity if the level of doping with elements of the first group is as high as 0.015%. Elements of the second group of impurities did not exert any significant effect on photoconductivity. The effect of impurities of the first group is attributed to occupation of vacant sites (formed as a result of removal of highly volatile Se and S atoms) by low concentrations of impurity atoms. The observed effect is related to the fact that substitutional atoms can preserve covalent bonds and to the small difference between atomic sizes and electron affinity for doping impurities and S and Se. Atoms of the second group of impurities lack these features.