Thin films of V(TCNE)x were deposited in ultrahigh vacuum using a film growth technique based on in situ chemical vapor deposition of tetracyanoethylene, TCNE, and bis-benzene vanadium, V(C6H6)2. The in situ preparation method enabled, for the first time, experimental analysis of oxygen-free films. X-ray magnetic circular dichroism measurements recorded at the V L2,3 edge confirmed room temperature magnetic ordering. A combination of conventional photoelectron spectroscopy (PES) and resonant photoemission (RPE) measured at the V L3 edge shows that the highest occupied electronic state is V(3d) derived. The rearrangements of the TCNE- related valence electronic states observed in PES and the evidence of V(3d) and TCNE- p(p*) orbital overlap contained in RPE spectra, indicate that strong, covalent type bonding occurs between the vanadium and the TCNE molecules. © 2006 The American Physical Society.