The preparation of the second generation iron(II) complex Fe(hfa)2·TMEDA (hfa=1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, TMEDA= N,N,N′,N′-tetramethylethylenediamine) is performed by reacting iron(II) chloride with Hhfa and TMEDA in two subsequent steps. Density functional theory data show that the compound possesses a distorted octahedral geometry, with the two β-diketonate ligands in a cis configuration. The complex mass transport properties and fragmentation pattern are investigated by thermal analyses and electron impact mass spectrometry, respectively. In addition, its experimental and simulated IR spectra are presented. For the first time, Fe(hfa)2·TMEDA was successfully applied in the chemical vapor deposition (CVD) of iron oxide on Si(100). Structural, compositional and morphological analyses evidence the possibility of obtaining pure, single-phase and homogeneous β-Fe2O3 films.