Despite their strong implications for magmatic processes in the earth's interior and pressure-induced structural changes in other amorphous, covalent oxide materials, little is known, beyond the coordination numbers of the framework cations, about the structures of silicate melts and glasses at high pressure. Here, we use multinuclear (Al-27 and O-17) solid-state NMR and quantum chemical calculations to study the structures of silicate glasses quenched from melts at pressures up to 10 GPa in a multianvil apparatus. The pressure-induced changes in atomic configurations in the silicate melts include the formation of highly coordinated framework units such as Al-[5,Al-6] and Si-[5,Si-6] and bridging oxygens linking these framework units and the presence of nonbridging oxygens coordinated by network-modifying cations and Si-[5,Si-6]. The proportion of high-pressure configurations such as Al-[5,Al-6]-O-Si-[4] increases with pressure, but the fraction of nonbridging oxygen (Na-O-Si-[4] decreases with pressure, leading to an increase of polymerization in melts. In bridging and nonbridging oxygens and highly coordinated framework units, structurally relevant NMR parameters (e.g., the isotropic chemical shift, delta(iso) and quadrupolar coupling product, P-q) show a pressure dependence. Quantum chemical calculations for model silicate clusters show that O-17 delta(iso) for ([n])(Si,Al)-O-Si-[4] mainly increases with increasing coordination number n. Although O-17 delta(iso) appears to be affected by longer-range interactions, it shows relatively moderate positive correlation with the ([n])(Si Al)-O bond length and appears to decrease with the distance between Na and bridging oxygens. O-17 delta(iso) for each oxygen cluster (([n])(Si,Al)-O-Si-[4]) obtained from O-17 3QMAS (triple quantum magic-angle spinning) NMR also increases with coordination number n. This is consistent with quantum calculations, implying that the ([n])(Si,Al)-O bond length may increase while the Na-O distance decreases with pressure. Although the overall variation O-17 p(q) for each oxygen site is not significant, the O-17 P-q value of Si-[4]-O-Si-[4] seems to decrease with increasing pressure, suggesting that the Si-[4]-O-Si-[4] angle may decrease with densification. The Al-27 P-q for Al-[n] increases with increasing pressure, which implies that the distortion of the network unit increases with pressure. The widths of O-17 delta(iso) distributions for ([n])(Si,Al)-O-Si-[4] increase with increasing pressure, which implies that bond lengths and angle distributions get wider with pressure. This trend is also consistent with the increasing distortion of framework polyhedra, suggested by increases in Al-27 P-q with pressure. The topological entropy was introduced to quantify the degree of randomness in the distributions of internal variables such as bond angle and length.