Abstract: High-silica mesoporous (pore radii 1.5–1.6 nm, MIP and pore radii 18.4–25.2 nm, MAP) vitreous AgI-doped membranes of the Vycor type have been manufactured. Characterization of the mesoporous glass morphology carried out by scanning electron microscopy (SEM). Successful synthesis of AgI-doped mesoporous glasses was confirmed by X-ray fluorescence (XRF) spectroscopy and energy-dispersive X-ray (EDX) spectroscopy. For the first time a comprehensive study of structural characteristics and electrokinetic properties (surface conductivity, streaming potential) of the AgI-doped MIP and MAP glasses in NaNO ₃, KNO ₃ and AgNO ₃ solutions in the concentration range 0.1–0.0001 M have been performed. The electrokinetic potential (ζ-potential) was found by the streaming potential method taking into account the surface conductivity and the electric double layers (EDL) overlap. The results were compared with the ζ-potential calculated from the electrophoretic mobility of the particles (laser Doppler velocimetry). It has been established that the structure of EDL in membrane nanopores and on the open surface of the AgI-doped porous particle differ significantly—different signs of the streaming potentials (negative) and electrophoretic mobility (positive) were observed for the AgI-doped glasses in AgNO ₃ solution.