Epitaxial LiCoO2 films are synthesized using a sol–gel method. The precursors are aqueous solutions of acetates or nitrates of Li and Co with polyvinylpyrrolidone as a thickener. The LiCoO2 films prepared from the solutions by spin coating are epitaxially grown on sapphire (0001) substrates with c-axis orientation and in-plane alignment of LiCoO2 [ 1 1 ¯ 0 ] ‖sapphire [100]. A two-step heat treatment of the spin-coated films consisting of preheating on a hotplate at the crystallization temperature followed by a high-temperature treatment notably promotes the c-axis orientation. In addition, the crystal orientation is controllable on different planes of the SrTiO3 substrates; the LiCoO2 films are grown with epitaxial relationships of LiCoO2 (001)‖SrTiO3 (111), LiCoO2 (018)‖SrTiO3 (110), and LiCoO2 (104)‖SrTiO3 (100).