The photoexcitation of (NO)(2) at 242-221 nm is studied by photoion and photoelectron imaging. A broad and structureless absorption band starting at 41,300 +/- 300 cm(-1) is observed. Ionization via the excited state accesses predominantly a dissociative state of (NO)(2)(+). The broad kinetic energy distribution of the photoelectrons suggests that the excited state has a large valence component in the Franck-Condon region, and that the geometries of the excited neutral state and the dimer ion state differ markedly. We propose that the same 'bright' state of mixed valence/Rydberg character is accessed at 242-200 nm, in agreement with preliminary ab initio calculations. (C) 2004 Elsevier B.V. All rights reserved.