The structural (structural resistance coefficient, volume porosity, average pore radius, and specific surface area) and transport (specific electrical conductivity and counterion transport numbers) characteristics of high-silica micro- and macroporous glasses with different compositions (magnetite-free and magnetite- containing glasses) have been compared in solutions of an indifferent electrolyte (sodium chloride). It has been shown that the incorporation of iron(III) oxide into basic sodium-borosilicate glass changes the structure of the pore space of both microporous glasses produced by acidic leaching and macroporous glasses obtained from the microporous samples by additional alkaline treatment. Moreover, it has been found that the transport characteristics of microporous glasses with different compositions are similar, while, for magnetite- phase-containing macroporous glasses, the specific conductivity of a pore solution and counterion transport numbers are increased.