Liquid B2O3 represents an archetypical oxide melt with a superhigh viscosity at the melting temperature. We present the results of the in situ x-ray diffraction study and the in situ viscosity measurements of liquid B2O3 under high pressure up to 8 GPa. Additionally, the 11B solid state NMR spectroscopy study of B2O3 glasses quenched from the melt at five different pressures has been carried out. Taken together, the results obtained provide understanding of the nature of structural transformations in liquid B2O3. The fraction of the boroxol rings in the melt structure rapidly decreases with pressure. From pressures of about 4.5 GPa, four-coordinated boron states begin to emerge sharply, reaching the fraction 40%-45% at 8 GPa. The viscosity of the B2O3 melt along the melting curve drops by 4 orders of magnitude as the pressure increases up to 5.5 GPa and remains unchanged on further pressure increase.