The synthesis and characterization of five new and closely related homoleptic iron(II) β-ketoiminate complexes is reported. Molecular structures of compounds 1, 2, and 5 were determined by single-crystal XRD, which revealed monomeric four- and sixfold coordination, depending on the functionalized side chain. The stepwise elimination of the ligand from the complex observed by thermogravimetric analysis and the stability in solution are encouraging features for solution-based processing of hematite thin films. As a representative example, compound 1 was successfully employed in a straightforward spin-coating process. The fabricated iron oxide films were characterized in terms of their structure and phase by XRD and Raman spectroscopy, morphology by SEM, and composition by Rutherford backscattering spectrometry accompanied by nuclear reaction analysis, which revealed the formation of crystalline and stoichiometric α-Fe₂O₃ films.