The mechanism of secondary ions formation has been investigated during He+ bombardment of ionic-compound surfaces. The O+ ions desorb from the TiO2(110) surface via the potential emission as revealed from their energy and angular distributions, while very little O+ ejection occurs from the MgO(001), Al2O3(0001), and SiO2 surfaces. The O+ ion is caused by the antibonding state with the O 2s core hole and its decay via the intra-atomic Auger process, resulting from the strong O 2p-Ti 3d hybridization and the quasiresonant charge exchange between the He 1s and O 2s states.[S0031-9007(99)08458-6].