The work has studied an effect of a high DC field on the composition and properties of the subsurface region of a multicomponent silicate glass. The concentration of alkali ions in the subsurface glass region was shown to drastically decrease under the high electric field. This led to a change in the ion-exchange characteristics of glasses and their resistance to etching. The effect allows employing the poled regions of the glass surface as dielectric masks in the formation of gradient optical structures, as well as relief microstructures, e.g., channels for microfluidics, in glass substrates. The advantage of this approach is that there is no need in multiple lithography using liquid chemicals. This reduces the cost and makes this technological process environment friendly.