The possibilities to grow thin layers of high-k dielectric CeAlO3 by pulsed injection metal-organic chemical vapor deposition using different metal-organic (MO) precursors have been investigated. Three pairs of MO precursors were studied for the growth of the films: Ce (IV) and Al(III) 2,2,6,6-tetramethylheptane-3,5-dionates, Ce tetrakis(1-methoxy-2-methyl-2-propoxide)-diethylaluminumethoxide and tris(isopropylcyclopentadienyl)cerium-tris(diethylamino)aluminum. Under optimized conditions, all three pairs of investigated precursors enabled the growth of close to stoichiometric Ce–Al–O films at reasonably low temperatures, 400–450°C, however, crystalline CeAlO3 phase was not present in as-deposited layers. Films were grown on Si(100) and Si(100)/TiN substrates. Two kinds of TiN electrodes were used — amorphous TiN (15–30nm thick) and crystalline TiN (70–100nm thick) layers, grown by chemical vapor deposition and physical vapor deposition techniques, respectively. The pure tetragonal CeAlO3 phase was crystallized in films by a short annealing in Ar or N2 at 800–850°C. Required annealing conditions (temperature and annealing duration) depended on the selected precursors and substrates. Thermomechanical degradation of Si/TiN/Ce–Al–O structures was observed by Scaning Electron Microscopy after the annealing of the samples. Lower degradation degree was observed for structures with a thin amorphous TiN layer.