Abstract:The structure of chalcogenide glassy semiconductors in three-component systems of Ge-As-Se and AsSb-Se has been studied by means of both NQR (nuclear quadrupole resonance) and EPR (electron paramagnetic resonance) spectroscopy. It is investigated that in the glasses of both systems the value of the electric field gradient at the resonating nuclei grows with increasing concentration of the clusters As 2 Se 3 and Sb 2 Se 3 , thereby increasing the NQR resonance frequencies. It appears that for the Ge-As-Se system the structural transition from a two-dimensional to three-dimensional structure occurs at average coordination number¯ = 2.45. The EPR spectral parameters of glasses depend on the composition, the average coordination number and the temperature, and these are discussed. The effect of "ageing" for CGS (chalcogenide glassy semiconductors) of As-Sb-Se system due to partial crystallization of the sample is observed from the EPR spectra.