The effects of reheating temperature on Ni-rich LiNi0.865Co0.095Al0.04O2 (NCA) are investigated since reheating process is required during surface modification and removal of adhered water molecules. It is shown that reheating temperature can exert observable influences on the structure, morphology, and electrochemical performance of the as-prepared Ni-rich cathode materials. In this work, commercial precursors were calcinated and reheated at 300, 450, 600, and 750 °C. After that, they were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests. XRD results confirmed that the occupancy of Ni2+ in the Li layer first decreases and then increases with increasing reheating temperature, and variation of Li layer spacing follows the same trend. Increasing reheating temperature accelerates the aggregation of lithium-related compounds such as Li2CO3 and LiOH. Interestingly, as the reheating temperature increases to 750 °C, the sample reverted to a smooth-like morphology, with an increase in the amount of Ni3+ at the surface. A higher capacity with better cyclic performance can be attained for NCA when reheated at 750 °C. Hence, reheating Ni-rich cathodes at suitable temperature can result in promising electrodes with advanced electrochemical performance.