It is shown that the vacuum poling of soda-lime silicate glass followed by silverfor-sodium ion exchange results in the formation of silver nanoparticles (NPs) in subcathode region of the glass. The latter was confirmed by the presence of silver NPs’ localized surface plasmon resonance peak in optical absorption spectra of the samples. The NPs had grown in 2 μm thick subsurface region of the glass, which was confirmed by etching the cathode side of the sample.  The possibility of forming a 2D-structured pattern from silver NPs that repeats the relief of the cathode electrode used for poling, has also been demonstrated. A hypothesis about the reduction of silver ions during the ion exchange  by sodium atoms penetrated the glass from the cathode during poling in vacuum is proposed.