The predesigned single-source precursors [Ba{(mu-ddbfo)(2)InMe2}(2)] (1), [Me2In(mu-ddbfo)](2) (2), [Sr{(mu-ddbfo)(2)AlMe2}(2)] (4), and [Me2Al(mu-ddbfo)](2) (5) (ddbfoH = 2,3-dihydro-2,2-dimethylbenzofuran-7-ol) for spinel-like double oxides and group 13 oxide materials were prepared via the direct reaction of the homoleptic aryloxide [M(ddbfoH)(4)]-(ddbfo)(2)center dot ddbfoH (M = Ba2+, Sr2+ (3)) and InMe3 or AlMe3 in toluene. In all of the reactions, there was an organometallic-driven abstraction of the OH protons from the 7-benzofuranols in the Ba2+ and Sr2+ cation sphere. All compounds were characterized by elemental analysis, H-1 NMR, and FT-IR spectroscopy. In addition, the molecular structures of 1, 2, and 3 were determined by single-crystal X-ray diffraction. The oxide products derived from the compounds mentioned above were studied using elemental analysis, Raman spectroscopy, X-ray powder diffraction, and scanning and transmission electron microscopy equipped with an energy-dispersive spectrometer. Moreover, their specific surface area and mesopore size distribution were evaluated using nitrogen porosimetry. Preliminary investigations of the Eu-doped SrAl2O4 and In2O3 phosphors revealed that the oxides obtained could be considered as matrices for lanthanide ions.