The structural (structural resistance coefficient, bulk porosity, average pore radius, and specific surface area) and electrokinetic (surface conductivity and electrokinetic potential) characteristics of high-silica micro- and macroporous glasses produced from two-phase sodium borosilicate glass have been compared in solutions of an indifferent electrolyte (sodium chloride) and iron(III) chloride containing iron ions, which have a high specificity to silica surfaces. It has been shown that, in the presence of iron ions, the electrokinetic behavior of porous glasses is governed by two factors. First, the superequivalent adsorption of these ions in the Stern layer leads to positive values of the electrokinetic potential, and, second, their mobility in the pore space decreases, thereby resulting in the appearance of equilibrium solution concentration ranges, in which the specific conductivity of a pore solution becomes lower than that of a free solution.