We present computational discoveries of new structural phases of the B2O compound exhibiting novelbonding networks and electronic states at ambient and elevated pressures. Our advanced crystalstructure searches in conjunction with density functional theory calculations have identified anorthorhombic phase of B2O that is energetically stable at ambient pressure and contains an intriguingbonding network of icosahedral B12clusters bridged by oxygen atoms. As pressure increases above1.9 GPa, a structural transformation takes the orthorhombic B2O into a pseudo-layered trigonal phase.We have performed extensive studies to investigate the evolution of chemical bonds and electronicstates associated with the B12 icosahedral unit in the orthorhombic phase and the covalent B–O bondsin the trigonal phase. We have also examined the nature of the charge carriers and their coupling to thelattice vibrations in the newly identified B2O crystals. Interestingly, our results indicate that both B2Ophases become superconducting at low temperatures, with transition temperatures of 6.4 K and 5.9 K,respectively, in the ambient and high-pressure phase. The present findings establish new B2O phases andcharacterize their structural and electronic properties, which offer insights and guidance for explorationtoward further fundamental understanding and potential synthesis and application.