As-S chalcogenide glasses doped with Mn (1,2,5,8 %wt) and Cr (0.5 and 0.75 % wt) have been investigated by differential scanning calorimetry. The glass transition temperature Tg was determined for all compositions. Value of Tg is decreased with the increase of Mn or Cr content. Activation energy of glass transition was estimated by Kissinger’s formula. From Fourier Raman spectra information on the structural changes in As-S glasses doped by transition metals or rare earth elements was obtained. Introduction of such dopants leads to the concentration increase of non-stoichiometric molecular fragments (such as As4S4, etc.). Influence of transition metals dopants on the optical properties of As-S glass was studied in mid-infrared region. The intensity of vibrational absorption bands of various impurity structural fragments essentially depends on chemical composition of glasses. The observed changes are considered to be connected with the interaction of the part of introduced dopants with non-stoichiometric elements present in glass and inherent impurities of the host glass such as hydrogen and oxygen atoms. Raman spectra of the ternary compositions Ge-As-S have been investigated and influence of the addition of the third element on the spectra of binary glasses has been studied. Also optical properties of ternary Ge-AsS(Se) were studied. Data on the change of magnetic and luminescence properties of chalcogenide glasses with the introduction of transition metal and rare earth dopants are presented.