We observe and analyze a considerable enhancement of photoelectron intensity of the valence band features in solid B2O3 upon tuning the photon energy across the B 1s→π*2pz resonance. This enhancement is an evidence of the strong 2p electron correlations in pre-edge photoionization dynamics in boron oxide. Such strength of the correlation is unusual for a solid, whose valence band is composed of only s and p electrons. We assign these effects to the considerable spatial localization of the highest occupied and lowest unoccupied electronic states of boron oxide on the BO33- quasimolecular anion, as well as to the strong 2p electron coupling between them. Solid state effects in the electronic structure and B 1s→π* decay dynamics are found to be minor, while molecular effects of the BO33- fragment are dominating. © Physica Scripta 2005.