Abstract: Transport numbers of sodium, nickel, and lanthanum counterions have been studied in microporous (average pore radius is r = 2–3.4 nm) and macroporous (r = 16–27 nm) magnetite-free glasses and those containing magnetite in their matrices. It has been found that, in the case of microporous glasses, the relation between the transport numbers of the studied cations is primarily governed by the structure of secondary silica in pore channels. For membranes prepared from macroporous glasses, the transport numbers of the cations in the pore space depend on the surface charge magnitude and the structure of the electrical double layer.