LiCoO2 thin films with different orientations were fabricated by pulsed laser deposition, and Li-ion transfer at the interface between the electrolyte and a LiCoO2 thin film electrode was investigated. This study particularly focused on the effect of orientation on Li-ion transfer. The thin films were shown to be highly crystallized by X-ray diffraction. Charge transfer resistance ascribed to Li-ion transfer at the interface was observed by ac impedance spectroscopy. While charge transfer resistance was strongly influenced by the preferred orientation of LiCoO2 thin film, the activation energy evaluated from the temperature-dependence of Li-ion transfer resistance appeared to be independent of the orientation.