This work is focused on investigating the effect of Ag doping on the dielectric and structural properties of the As-S-Se glass system and their suitability for potential applications in optoelectronics, such as electronic and switching components. A series of glasses from the system Ag-x(As40S30Se30)(100-x) (x <= 5 at.% Ag) were prepared with melt-quenching technique. Morphological and compositional analysis was performed by scanning electron microscopy and energy-dispersive X-ray spectroscopy. Raman spectroscopy measurements have shown structural modifications of the glass network upon Ag doping, with creation of new Ag-(S,Se)-As structures, resulting in increased number of defect states. Variations in dielectric permittivity (epsilon ') and dielectric loss (epsilon '') were investigated in a wide frequency and temperature range, and explained by dominant dipolar and electronic polarization, as well as correlated with the observed structural changes. Improvement in dielectric properties is observed upon doping with Ag. Furthermore, the low dielectric tangent loss at high frequencies for all glassy samples points to a beneficial ability of the material to absorb energy of the external electric field. Good thermal stability of these glasses is confirmed by the calculated temperature coefficient of the dielectric permittivity. Density of localized states in all glasses was determined from AC conductivity and the dielectric tangent loss using a correlated barrier hopping model, and found to increase with Ag concentration. The overall results suggest that Ag doping enhances the electrical and optical quality of this type of glasses, making them suitable as nonlinear optical materials and their applications in devices.