LiCoO₂ films were prepared on polycrystalline Al₂O₃ substrates by metal organic chemical vapor deposition (MOCVD), and the effect of the Li to Co source vapor ratio (R_Li/Co) and substrate temperature (T_sub) on the phases, orientation, morphology, and deposition rates were investigated. At R_Li/Co > 2.0, Li₂CO₃, Li_xCo_1−xO, and a LiCoO₂–CoO solid solution were co-deposited with LiCoO₂, whereas Co₃O₄ was co-deposited with LiCoO₂ at R_Li/Co < 0.7. Single-phase LiCoO₂ films were obtained in the R_Li/Co range of 0.7–2.0 at T_sub > 873 K. Rutherford backscattering spectrometry revealed that single-phase LiCoO₂ film had uniform and stoichiometric composition. The orientation of single-phase LiCoO₂ films changed from (003) to (104) and (012) with increasing T_sub at R_Li/Co ~ 1.0. LiCoO₂ film co-deposited with Co₃O₄ at R_Li/Co = 0.4 showed significant (101) orientation. The (003)-oriented LiCoO₂ had a flat surface with hexagonal faceted texture, whereas the (101)- and (104)-oriented LiCoO₂ had platelet grains in which the plate faces were tilted relative to the substrate surface. The highest deposition rate of single-phase LiCoO₂ film was 10–20 µm h⁻¹, which was 100 times greater than that reported in the literature.