A simple method has been employed to prepare pillared layered Li1−2x Ca x CoO2 cathode materials by cationic exchange under hydrothermal conditions. The synthesized materials were characterized by means of X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), field emission scanning electron microscope (FE-SEM) and galvanostatic charge–discharge cycling. The XRD data of the products show that they are single phases and retain the layered α-NaFeO2 type structure. The FE-SEM images of the materials prepared by hydrothermal method show uniform small particles, and the particle size of the materials is about 200nm. The initial discharge specific capacities of layered LiCoO2 and pillared layered Li0.946Ca0.027CoO2 cathode materials calcined at 800°C for 5h within the potential range of 3.0–4.3V (vs. Li+/Li) are 144.6 and 142.3mAhg−1, respectively, and both materials retain good charge–discharge cycling performance. However, with increasing upper cutoff voltage, the pillar effect of Ca2+ in Li1−2x Ca x CoO2 becomes more significant. The pillared layered Li0.946Ca0.027CoO2 has a higher capacity with an initial discharge specific capacity of 177.9 and 215.8mAhg−1 within the potential range of 3.0–4.5 and 4.7V (vs. Li+/Li), respectively, and retains good charge–discharge cycling performance.