Rare-earth iron oxides (RFe2O4) have attracting attention as new electronic device materials because of their numerous functionalities, such as electronic ferroelectricity, ferrimagnetism, and high infrared absorption. In this paper, nearly monophasic YbFe2O4 films were prepared on alpha-Al2O3 (001) substrates by the spin coating method using an aqueous-based YbFe2O4 solution. The solution was composed of a stoichiometric ratio of Yb(CH3COO)(3) and Fe(NO3)(3) with excess chelating agents. After heat treatment above 800 degrees C, well-crystallized and highly (001)-oriented YbFe2O4 started to epitaxially form on the substrate under controlled oxygen partial pressure with H-2/CO2 gas mixtures. X-ray pole figure analysis confirmed the following epitaxial relationship: YbFe2O4[100](001)//alpha-Al2O3[100](001). Moreover formation of an Fe3O4 interracial layer between YbFe2O4 and alpha-Al2O3 was detected by high-resolution transmission electron microscopy. Presence of the Fe3O4 interracial layer seemed to release the lattice misfit with the substrate. The Fe2+/Fe3+ ratio in the obtained YbFe2O4 films was nearly stoichiometric and the indirect bandgap assigned to Fe2+ -> Fe3+ charge transfer excitation was found to be similar to 0.4 eV by optical spectroscopy. A clear magnetic transition from the paramagnetic state to the ferrimagnetic state occurred at similar to 230 K. (C) 2016 Author(s).