Electronic stabilities, structures, properties, and spectroscopic constants of the halogen oxide dianions OBr 2− and OCl 2− and their singly charged anions which are of astrophysical and laboratory interests have been studied. The X 2 Σ states of OBr 2− and OCl 2− are metastable with PECs having smooth wells with minima located at R=1.859Å and 1.776Å, and Coulomb barriers of 40402.54987cm −1 and 43746.63462cm −1 heights located at R RCB =2.100Å and 1.922Å, respectively, both without any vibrational states. While, the B 2 Σ state of OBr 2− and the A 2 Σ state of OCl 2− are metastable with PECs having wells deep enough to suite several bound states, with minima located at R e =1.773Å and 1.6430Å, and Coulomb barriers of 191437.45813cm −1 and 180550.70294cm −1 heights located at R RCB =2.658Å and 2.4480Å, with D e =1.26470eV and 1.60837eV, respectively. The OBr − and OCl − singly charged anions are stable in their ground states. Based on the calculated Frank–Condon factors, it is concluded that metastable excited state OBr 2− and OCl 2− dianions and ground state OBr − and OCl − singly charged anions can be formed via electron capture processes.