In this study, we carried out the analysis of the impact melt vein glasses from the Kara impact crater (Russia) in comparison to low-pressure impact melt glasses (tektites) of the Zham-anshin crater (Kazakhstan). ²⁷Al, ²³Na, and ²⁹Si MAS NMR spectra of the samples of these glasses were analyzed. The samples of the natural glass contained inclusions of crystalline phases, para-magnetic elements that greatly complicate and distort the NMR signals from the glass phase itself. Taking into account the Mossbauer distribution of Fe in these glasses, the analysis of the spectra of MAS NMR of glass network-former (Si, Al) and potential network-modifiers (Na) of nuclei leads to the conclusion that the Kara impact melt vein glasses are characterized by complete polymerization of (Si,Al)O4 tetrahedral structural units. The NMR features of the glasses are consistent with the vein hypothesis of their formation under conditions of high pressures and temperatures resulting in their fluidity, relatively slow solidification with partial melt differentiation, polymerization, and precipitation of mineral phases as the impact melt cools. The 70 Ma stability of the Kara impact vein glass can be explained by the stabilization of the glass network with primary fine-dispersed pyroxene and coesite precipitates and by the high polymerization level of the impact glass.