AlN ceramics exhibit good physical and chemical properties and are ideal materials for the dielectric layer of electrostatic chucks. However, they cannot generate a strong J−R-type electrostatic adsorption force because of their high resistivity. Therefore, adding other substances is necessary to regulate the electrical properties and enable their application. In this study, AlN ceramics were prepared using hot-pressed sintering with 0.2 wt% CaO as an additive at a sintering temperature range of 1700–1900 °C. The effects of CaO doping on the phase composition, microstructure, electrical properties, and thermal conductivity of the AlN ceramics were systematically investigated. The addition of CaO not only enhanced the sintering process of the AlN ceramics, but also significantly reduced the electrical resistivity and increased the thermal conductivity. The relative density of CaO-doped AlN ceramics reached 98.88 % at 1700 °C, with a thermal conductivity of 81.51 W•m−1•K−1. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and AC impedance spectroscopy were used to analyze the impurities and defects in the AlN ceramics. The lattice parameters and fitting grain resistance indicated that the CaO-doped AlN presented a higher lattice oxygen concentration, increasing the concentration of Al vacancies and electrons. Moreover, the level of dissolved oxygen could be controlled by altering the sintering temperature, resulting in AlN ceramics with electrical resistivity ranging from 8.1×106 to 1.7×1012 Ω•cm. Further research was conducted to investigate the effect of the electrical resistivity of AlN ceramics on the J−R-type electrostatic adsorption force, and it was found that AlN ceramics with a specific resistivity of 109 Ω•cm exhibited the highest electrostatic adsorption of 351.7 g/cm2.