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It is shown experimentally that electron irradiation of sodium–silicate glasses makes possible the control of the subsequent ion exchange Ag + ↔ Na + process in a salt melt. The reason of this effect is the negatively charged regions formation in a glass volume during electron irradiation. The electric field, produced by these regions in glass volume, results in positive Na + ions field migration into them. The spatial redistribution of Na + ions results in the decrease of the ion exchange efficiency, or the ion exchange can be even blocked. This led to the decrease of the luminescence intensity of neutral silver molecular clusters in the irradiated zone, and effect on the silver nanoparticles formation during the subsequent thermal treatment. The observed effects can be used for the control of ion exchange processes during integrated optics devices fabrication, and for the electron-beam recording of optical information. [ABSTRACT FROM AUTHOR]