O4-type LiCoO2 as a third polymorph of LiCoO2 is prepared by an ion-exchange method in aqueous media from OP4-[Li, Na]CoO2, which has an intergrowth structure of O3-LiCoO2 and P2-Na0.7CoO2. O4-type LiCoO2 is characterized by synchrotron X-ray diffraction, neutron diffraction, and X-ray absorption spectroscopy. Structural characterization reveals that O4-type LiCoO2 has an intergrowth structure of O3- and O2-LiCoO2 with stacking faulted domains. Three LiCoO2 polymorphs are formed from the close-packed CoO2 layers, which consist of edge-shared CoO6 octahedra, whereas the oxide-ion stacking is different: cubic in the O3-phase, cubic/hexagonal in the O2-phase, and alternate O3 and O2 in the O4-phase. Structural analysis using the DIFFaX program suggests that the O4-phase consists of approximately 30% of O12-domains, while stacking faults are not evidenced for O2-phase. The results suggest that a nucleation process for Na/Li ion-exchange kinetically dominates a growth process of ideal O4-domains because the presence of CoO2-Li-CoO2 blocks as O3-domains could be expected to prevent through-plane interaction of Na layers. Electrochemical behavior and structural transition processes for three LiCoO2 polymorphs are compared in Li cells. A new phase, OT(#)4-type Li0.5CoO2, is first isolated as an intergrowth phase of O3- and T(#)2-Li0.5CoO2. However, some deviations from ideal behavior as the O2/O3-intergrowth phase are also noted, presumably because of the existence of stacking faults.