An adduct of Co(II) 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate with N,N,N',N'-tetramethylethylenediamine is synthesized by a simple procedure and, for the first time, thoroughly characterized by several analytical methods in order to elucidate its structure (single-crystal X-ray diffraction), chemical composition (elemental analyses, FT-IR), optical properties (UV-vis absorption spectroscopy), thermal behavior (thermogravimetric analysis and differential scanning calorimetry), and fragmentation pathways (electrospray ionization mass spectrometry and tandem mass spectrometry). The target complex is monomeric with a pseudo-octahedral Co(II) core and presents a clean decomposition pathway and a high volatility at moderate temperatures. Preliminary chemical vapor deposition (CVD) experiments highlight its very promising features as a CVD/atomic layer deposition molecular source for cobalt oxide nanosystems.