The direct Coulomb explosion of N2O2+ has been investigated experimentally after double-ionization by a single extreme ultraviolet (EUV) photon with an energy of～38.5 eV. From the ion–ion time-of-fl ight coincidence spectrum, the de-nitrogenation (N2O2+→N++NO+) and de-oxygenation (N2O2+→O++N+2 ) photodissociation channels of N2O2+are unequivocally identified. The measured kinetic energy release (KER) distribution of the de-nitrogenation channel presents a major peak accompanied by a shoulder structure. We find that the major peak can be attributed to the direct photodissociation of the 11?and 11Σ+states, while the shoulder structure should be ascribed to the predissociation of the 11?and 11Σ+states via 13Πstate.