Molecular dissociation following radiative decay of O 1s hole states in CO2 has been studied by detecting photoions in coincidence with undispersed soft X-ray emission. The production of ions after radiative decay is observed to increase from practically nothing at the O 1s -> pi* excitation to the appearance of CO2+, CO+, C+ and O+ ions when core-valence double excitations and O 1s shake-up transitions are induced. De-excitation pathways involving radiative decay from different core-hole states are discussed in order to interpret the results. A weak CO22+ signal is attributed to the radiative Auger effect. (C) 2012 Elsevier B.V. All rights reserved.