Room temperature ferromagnetic ordering is reported in Ni–tetracyanoethylene (TCNE) thin films fabricated on Au substrates using physical vapor deposition (PVD) under ultra high vacuum conditions. This technique enables the preparation of very clean films without having any kind of contamination from oxygen-containing species, solvents or precursor molecules. Film stoichiometry was obtained from X-ray photoelectron spectroscopy (XPS) measurements. XPS derived stoichiometry points to a 1 : 2 ratio between Ni and TCNE resulting in Ni(TCNE)x, x ≈ 2. No evidence of pure Ni metal in the in situ grown films was present in the XPS or the ultraviolet photoelectron spectroscopy (UPS) measurements within the detection limits of the techniques.