Geochemists often debate the conditions in which Al3+ may become 6-coordinated in molten silicates and how such liquid structures are related to those of coexisting crystal phases1–4. To date no experimental evidence for the occurrence of Al3+ in this coordination state has been presented and computer simulation studies have suggested that pressures exceeding 100 kbar may be required for the 4→6 conversion5,6. To examine this question in the laboratory, we have taken advantage of the ability of the glass transition to freeze the structural equilibrium of a high-pressure melt and preserve it for subsequent examination in ambient conditions. Glasses of albite composition have been prepared by quenching melts under pressures of 0–80 kbar (0–8 GPa). The Al3+ coordination has been determined by 27Al solid-state NMR spectrometry. We find that the 4-coordinated state is retained to pressures well beyond 30 kbar. A new peak at −16 p.p.m. relative to Al(H2O)3+6, which we associate with octahedral Al3+ appears weakly at 60 kbar and becomes a prominent feature of the spectrum at 80 kbar.