The molecule-based magnet V (TCNE)x, with TCNE=tetracyanoethylene, x˜2, shows an exceptionally high magnetic ordering temperature of about 400 K. With the aim to shed light on the origins of the robust magnetic ordering interactions, we have characterized the chemical bonding in V (TCNE)x thin films, prepared by an in situ chemical vapor deposition method, using photoelectron spectroscopy, x-ray absorption spectroscopy (XAS), and x-ray magnetic circular dichroism (XMCD). The XAS and XMCD results were interpreted by ligand field multiplet and charge transfer multiplet calculations, which show that the V-NC bonds are characterized by a large crystal field parameter 10Dq=2.3 eV and strong ligand to metal charge transfer effects, resulting in a hybrid V (3d) -CN ground state given by 60% 3 d3 and 40% 3 d4 L, where L is a hole on the cyano ligands. © 2007 The American Physical Society.