This work is devoted to the preparation of dense Ag+ conductive ceramic solid electrolytes in the Ag6PS5I‒Ag7GeS5I system and to the study of their electrical and optical properties. Using the non-destructive and simple method of optical diffuse reflectance spectroscopy, the value of the optical pseudogap energy of the Ag6+x(P1-xGex)S5I (x=0, 0.25, 0.5, 0.75, 1.0) solid solutions was obtained using the Kubelka-Munk function with the application of Tauc's graphic method. As a result of the performed mathematical analysis and graphic processing, it was established that the quaternary chalcohalogenides Ag6PS5I, Ag7GeS5I and solid solutions Ag6+x(P1-xGex)S5I (x=0.25, 0.5, 0.75) belong to direct-band semiconductors characterized by a forbidden optical transition . The study of electrical conductivity of Ag6+x(P1-xGex)S5I solid solutions (x=0, 0.25, 0.5, 0.75, 1.0) was carried out by the method of impedance spectroscopy, in the frequency 1×101–3×105 Hz and temperature 293–383 K ranges. For all ceramic materials prepared on the basis of Ag6+x(P1-xGex)S5I (x=0, 0.25, 0.5, 0.75, 1.0) solid solutions, an increase in the values of total electrical conductivity was observed, which is characteristic of materials with ionic electrical conductivity in the solid state.
 Keywords: argyrodites; solid solutions; ceramic; impedance spectroscopy; conductivity; optical properties; optical pseudogap.