Charged molecular species have special roles in upper atmosphere and interstellar regions. An ab initio calculation for NCO2+ electronic structures by cc-pVQZ/CASSCF/MRCI method is presented. The potential energy surfaces of low-lying states of NCO2+ have been explored. The ground state X (2)Pi and the lowest excited state a (4)Sigma are metastable with a major collinear dissociation channel into N+ (X P-3(g)) + CO+ (X (2)Sigma(+)). For the excited states from 3 to 8 eV the pre-dissociation processes are dominant while the states above 8 eV are repulsive. Several crossings, avoided crossings and conical intersections for NCO2+ have also been assigned. (c) 2013 Elsevier B.V. All rights reserved.