The unoccupied electronic structure of the organic-based magnet V(TCNE)(x) (TCNE = tetracyanoethylene, x similar to 2) has been studied with near edge X-ray absorption fine structure (NEXAFS) and with photoelectron spectroscopy (PES). By studying V(TCNE), upon sodium-doping, the electron-accepting state, i.e., the lowest unoccupied molecular orbital (LUMO) of V(TCNE)(x) was shown mainly to be localized on (TCNE)(-)-units in contrast to the hole-accepting state, i.e., the highest occupied molecular orbital (HOMO), which previously was assigned primarily to be V(3d)-derived. This study also showed that there are trap states for electron transport located below the (TCNE)(2-) level, likely leading to decreased electron mobility. (c) 2007 Elsevier B.V. All rights reserved.