The pressure-induced structural evolutions of boron-bearing model rhyolitic melts under high pressures enable to infer the detailed geochemical processes (melting and fluid-rock-melt interactions) occurring in Earth interiors and to control the melt properties (viscosity and the boron isotope composition, delta B-11) of complex magmatic melts, providing insights into the boron cycle toward the deeper part of the upper mantle (similar to 10 GPa). Despite the importance, the structures of multicomponent boron-bearing silicate melts above 3 GPa are currently unavailable. Here, we explore the structures, particularly, coordination transformation of constituent elements in boron-bearing nepheline and albite glasses - a model rhyolitic melts - upon compression to a depth of similar to 270 km (similar to 9.2 GPa) in the mantle using multi-nuclear solid-state nuclear magnetic resonance (NMR) spectroscopy. The results showed that the conversion of B-[3] into B-[4] is prominent upon compression up to 6 GPa. In contrast, the formation of Al-[5,Al-6] is accompanied by the formation of oxygen tricluster above 6 GPa, where all the nonbridging oxygens are consumed. We quantify how the melt composition affects tendency to form highly coordinated B, Al, and Si upon compression. Particularly, the increase in the ([4]) B population tends to be larger for the glasses with low Si content as pressure increases to 9.2 GPa. We reveal the relationship between such structural adaptations of the compressed melts at high pressure and the melt properties, including viscosity and element partition coefficient in boron-bearing melts. The current NMR results also unravel the structural origins of B-11/B-10 ratios in rhyolitic melts at high pressure. Considering a preferential partitioning of B-10 to B-[4], an increase in B-[4] population in the melts leads to an pressure-induced enrichment of B-10. As the increase in Si/B ratio in the melts tends to decrease the pressure-induced increase in B-[4] fraction, the contribution of boron coordination transformation on the B-11/(10) B ratios in silicate melt would be somewhat minor in deep mantle melts with increasing Si content. The detailed boron environments in rhyolitic melts at high pressure yield useful constraints for the isotope composition (B-11/B-10) of dense mantle melts, thereby enabling quantification of deep boron cycle. (C) 2022 Elsevier Ltd. All rights reserved.