Novel solution precursors for CeO2 buffer layers, based on mixed-ligand hydroxocomplexes of lanthanide acetates and nitrates with monoethanolamine (MEA) and diglyme, acting as both ligands and solvents, have been developed. The formation of mixed-ligand Ce(IV) complexes in both liquid and transparent gel precursors have been confirmed by electrospray ionization−mass spectroscopy (ESI-MS) and 1H nuclear magnetic resonance (NMR) spectroscopy. The features of thermal decomposition of gel precursor samples were studied using thermogravimetry (TG) and differential thermogravimetry (DTG) analyses in air and in argon. The advantages of the new precursors are the accessibility of high concentrations, stability, and excellent wetting behavior of Ni−5 at.% W substrates. Various elements can be easily incorporated into them as dopants, as was shown on an example of La3+. Epitaxial CeO2 and CeO2(La) films were deposited on Ni−W cube-textured tapes from developed solutions via the metal-organic chemical solution deposition (MOCSD) method. Incorporation of La3+ into the buffer layer leads to improvement in the oxide’s texture and the film’s surface.