Deciphering the structural evolution in irreversibly densified oxide glasses is crucial for fabricating functional glasses with tunable properties and elucidating the nature of pressure-induced anomalous plastic deformation in glasses. High-resolution NMR spectroscopy quantifies atomic-level structural information on densified glasses; however, its application is limited to the low-pressure range due to technical challenges. Here, we report the first high-resolution NMR spectra of oxide glass compressed by diamond anvil cells at room temperature, extending the pressure record of such studies from 24 to 65 GPa. The results constrain the densification path through coordination transformation of Al cations. Based on a statistical thermodynamic model, the stepwise changes in the Al fractions of oxide glasses and the effects of network polymerization on the densification paths are quantified. These results extend the knowledge on densification of the previously unattainable pressure conditions and contribute to understanding the origin of mechanical strengthening of the glasses.