LiCoO2 thin films were prepared by pulsed laser deposition (PLD) on Pt/Ti/SiO2/Si (Pt) and Au/MgO/Si (Au) substrates, respectively. Crystal structures and surface morphologies of thin films were investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The LiCoO2 thin films deposited on the Pt substrates exhibited a preferred (003) texture with smooth surfaces while the LiCoO2 thin films deposited on the Au substrates exhibited a preferred (104) texture with rough surfaces. The electrochemical properties of the LiCoO2 films with different textures were compared with charge–discharge, dQ/dV, and Li diffusion measurements (PITT). Compared with the (104)-textured LiCoO2 thin films, the (003)-textured thin films exhibited relatively lower electrochemical activity. However, the advantage of the (104)-textured film only remained for a small number of cycles due to the relatively faster capacity fade. Li diffusion measurements showed that the Li diffusivity in the (003)-textured film is one order of magnitude lower than that in the (104)-textured film. As discussed in this paper, we believe that Li diffusion through grain boundaries is comparable to or even faster than Li diffusion through the grains.